Kinetic Molecular Theory of Gases

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To better understand the molecular origins of the ideal gas law,

PV=nRT(1.1)(1.1)PV=nRT

the basics of the Kinetic Molecular Theory of Gases (KMT) should be understood. This model
is used to describe the behavior of gases. More specifically, it is used to explain macroscopic
properties of a gas, such as pressure and temperature, in terms of its microscopic components,
such as atoms. Like the ideal gas law, this theory was developed in reference to ideal gases,
although it can be applied reasonably well to real gases.

In order to apply the kinetic model of gases, five assumptions are made:

1. Gases are made up of particles with no defined volume but with a defined mass. In other
words their volume is miniscule compared to the distance between themselves and other
molecules.
2. Gas particles undergo no intermolecular attractions or repulsions. This assumption
implies that the particles possess no potential energy and thus their total energy is simply
equal to their kinetic energies.
3. Gas particles are in continuous, random motion.
4. Collisions between gas particles are completely elastic. In other words, there is no net
loss or gain of kinetic energy when particles collide.
5. The average kinetic energy is the same for all gases at a given temperature, regardless of
the identity of the gas. Furthermore, this kinetic energy is proportional to the absolute
temperature of the gas.

Temperature and KMT

The last assumption can be written in equation form as:

KE=12mv2=32kBT(1.2)(1.2)KE=12mv2=32kBT

where
 kBkB is Boltzmann's constant (k = 1.38110 m kg s K ) and
B
-23 2 -2 -1

TT is the absolution temperature (in Kelvin)

This equation says that the speed of gas particles is related to their absolute temperature. In other
words, as their temperature increases, their speed increases, and finally their total energy
increases as well. However, it is impossible to define the speed of any one gas particle. As such,
the speeds of gases are defined in terms of their root-mean-square speed.

Pressure and KMT

The macroscopic phenomena of pressure can be explained in terms of the kinetic molecular
theory of gases. Assume the case in which a gas molecule (represented by a sphere) is in a box,
length L (Figure 1). Through using the assumptions laid out above, and considering the sphere is
only moving in the x-direction, we can examine the instance of the sphere colliding elastically
with one of the walls of the box.

Figure 1

The momentum of this collision is given by p=mv, in this case p=mvx, since we are only
considering the x dimension. The total momentum change for this collision is then given by

mvxm(vx)=2mvx(1.3)(1.3)mvxm(vx)=2mvx

Given that the amount of time it takes between collisions of the molecule with the wall is L/vx we
can give the frequency of collisions of the molecule against a given wall of the box per unit time
as vx/2L. One can now solve for the change in momentum per unit of time:

(2mvx)(vx/2L)=mv2x/L(1.4)(1.4)(2mvx)(vx/2L)=mvx2/L
Solving for momentum per unit of time gives the force exerted by an object (F=ma=p/time).
With the expression that F=mvx2/L one can now solve for the pressure exerted by the molecular
collision, where area is given as the area of one wall of the box, A=L2:

P=FA(1.5)(1.5)P=FA

P=mv2x[L(L2)(1.6)(1.6)P=mvx2[L(L2)

The expression can now be written in terms of the pressure associated with collisions
from N number of molecules:

P=Nmv2xV(1.7)(1.7)P=Nmvx2V

This expression can now be adjusted to account for movement in the x, y and z directions by
using mean-square velocity for three dimensions and a large value of N. The expression now is
written as:

P=Nmv23V(1.8)(1.8)P=Nmv23V

This expression now gives pressure, a macroscopic quality, in terms of atomic motion. The
significance of the above relationship is that pressure is proportional to the mean-square velocity
of molecules in a given container. Therefore, as molecular velocity increases so does the pressure
exerted on the container.

The Kinetic Molecular Theory Postulates

The experimental observations about the behavior of gases discussed so far can be
explained with a simple theoretical model known as the kinetic molecular theory.
This theory is based on the following postulates, or assumptions.

1. Gases are composed of a large number of particles that behave like hard,
spherical objects in a state of constant, random motion.

2. These particles move in a straight line until they collide with another particle or
the walls of the container.

3. These particles are much smaller than the distance between particles. Most of
the volume of a gas is therefore empty space.

4. There is no force of attraction between gas particles or between the particles

and the walls of the container.
 5. Collisions between gas particles or collisions with the walls of the container are
perfectly elastic. None of the energy of a gas particle is lost when it collides
with another particle or with the walls of the container.

6. The average kinetic energy of a collection of gas particles depends on the

temperature of the gas and nothing else.

The assumptions behind the kinetic molecular theory can be illustrated with the
apparatus shown in the figure below, which consists of a glass plate surrounded by
walls mounted on top of three vibrating motors. A handful of steel ball bearings are
placed on top of the glass plate to represent the gas particles.

When the motors are turned on, the glass plate vibrates, which makes the ball bearings
move in a constant, random fashion (postulate 1). Each ball moves in a straight line
until it collides with another ball or with the walls of the container (postulate 2).
Although collisions are frequent, the average distance between the ball bearings is
much larger than the diameter of the balls (postulate 3). There is no force of attraction
between the individual ball bearings or between the ball bearings and the walls of the
container (postulate 4).

The collisions that occur in this apparatus are very different from those that occur
when a rubber ball is dropped on the floor. Collisions between the rubber ball and the
floor are inelastic, as shown in the figure below. A portion of the energy of the ball is
lost each time it hits the floor, until it eventually rolls to a stop. In this apparatus, the
collisions are perfectly elastic. The balls have just as much energy after a collision as
before (postulate 5).

Any object in motion has a kinetic energy that is defined as one-half of the product of
its mass times its velocity squared.

KE = 1/2 mv2

At any time, some of the ball bearings on this apparatus are moving faster than others,
but the system can be described by an average kinetic energy. When we increase the
"temperature" of the system by increasing the voltage to the motors, we find that the
average kinetic energy of the ball bearings increases (postulate 6).
 How the Kinetic Molecular Theory Explains the Gas Laws

The kinetic molecular theory can be used to explain each of the experimentally
determined gas laws.

The Link Between P and n

The pressure of a gas results from collisions between the gas particles and the walls of
the container. Each time a gas particle hits the wall, it exerts a force on the wall. An
increase in the number of gas particles in the container increases the frequency of
collisions with the walls and therefore the pressure of the gas.

Amontons' Law (P T)

The last postulate of the kinetic molecular theory states that the average kinetic energy
of a gas particle depends only on the temperature of the gas. Thus, the average kinetic
energy of the gas particles increases as the gas becomes warmer. Because the mass of
these particles is constant, their kinetic energy can only increase if the average
velocity of the particles increases. The faster these particles are moving when they hit
the wall, the greater the force they exert on the wall. Since the force per collision
becomes larger as the temperature increases, the pressure of the gas must increase as
well.

Boyle's Law (P = 1/v)

Gases can be compressed because most of the volume of a gas is empty space. If we
compress a gas without changing its temperature, the average kinetic energy of the gas
particles stays the same. There is no change in the speed with which the particles
move, but the container is smaller. Thus, the particles travel from one end of the
container to the other in a shorter period of time. This means that they hit the walls
more often. Any increase in the frequency of collisions with the walls must lead to an
increase in the pressure of the gas. Thus, the pressure of a gas becomes larger as the
volume of the gas becomes smaller.

Charles' Law (V T)

The average kinetic energy of the particles in a gas is proportional to the temperature
of the gas. Because the mass of these particles is constant, the particles must move
faster as the gas becomes warmer. If they move faster, the particles will exert a greater
force on the container each time they hit the walls, which leads to an increase in the
pressure of the gas. If the walls of the container are flexible, it will expand until the
pressure of the gas once more balances the pressure of the atmosphere. The volume of
the gas therefore becomes larger as the temperature of the gas increases.

Avogadro's Hypothesis (V N)

As the number of gas particles increases, the frequency of collisions with the walls of
the container must increase. This, in turn, leads to an increase in the pressure of the
gas. Flexible containers, such as a balloon, will expand until the pressure of the gas
inside the balloon once again balances the pressure of the gas outside. Thus, the
volume of the gas is proportional to the number of gas particles.

Dalton's Law of Partial Pressures (Pt = P1 + P2 + P3 + ...)

Imagine what would happen if six ball bearings of a different size were added to
the molecular dynamics simulator. The total pressure would increase because there would
be more collisions with the walls of the container. But the pressure due to the
collisions between the original ball bearings and the walls of the container would
remain the same. There is so much empty space in the container that each type of ball
bearing hits the walls of the container as often in the mixture as it did when there was
only one kind of ball bearing on the glass plate. The total number of collisions with
the wall in this mixture is therefore equal to the sum of the collisions that would occur
when each size of ball bearing is present by itself. In other words, the total pressure of
a mixture of gases is equal to the sum of the partial pressures of the individual gases.

Graham's Laws of Diffusion and Effusion

A few of the physical properties of gases depend on the identity of the gas. One of
these physical properties can be seen when the movement of gases is studied.

In 1829 Thomas Graham used an apparatus similar to the one shown in the figure
below to study the diffusion of gases the rate at which two gases mix. This
apparatus consists of a glass tube sealed at one end with plaster that has holes large
enough to allow a gas to enter or leave the tube. When the tube is filled with H 2 gas,
the level of water in the tube slowly rises because the H 2 molecules inside the tube
escape through the holes in the plaster more rapidly than the molecules in air can enter
the tube. By studying the rate at which the water level in this apparatus changed,
Graham was able to obtain data on the rate at which different gases mixed with air.
Graham found that the rates at which gases diffuse is inversely proportional to the
square root of their densities.

This relationship eventually became known as Graham's law of diffusion.

To understand the importance of this discovery we have to remember that equal

volumes of different gases contain the same number of particles. As a result, the
number of moles of gas per liter at a given temperature and pressure is constant,
which means that the density of a gas is directly proportional to its molecular weight.
Graham's law of diffusion can therefore also be written as follows.

Similar results were obtained when Graham studied the rate of effusion of a gas,
which is the rate at which the gas escapes through a pinhole into a vacuum. The rate
of effusion of a gas is also inversely proportional to the square root of either the
density or the molecular weight of the gas.

Graham's law of effusion can be demonstrated with the apparatus in the figure
below. A thick-walled filter flask is evacuated with a vacuum pump. A syringe is filled
with 25 mL of gas and the time required for the gas to escape through the syringe
needle into the evacuated filter flask is measured with a stop watch.

As we can see when data obtained in this experiment are graphed in the figure below,
the time required for 25-mL samples of different gases to escape into a vacuum is
proportional to the square root of the molecular weight of the gas. The rate at which
the gases effuse is therefore inversely proportional to the square root of the molecular
weight. Graham's observations about the rate at which gases diffuse (mix) or effuse
(escape through a pinhole) suggest that relatively light gas particles such as
H2 molecules or He atoms move faster than relatively heavy gas particles such as
CO2 or SO2 molecules.

The Kinetic Molecular Theory and Graham's Laws

The kinetic molecular theory can be used to explain the results Graham obtained when
he studied the diffusion and effusion of gases. The key to this explanation is the last
postulate of the kinetic theory, which assumes that the temperature of a system is
proportional to the average kinetic energy of its particles and nothing else. In other
words, the temperature of a system increases if and only if there is an increase in the
average kinetic energy of its particles.

Two gases, such as H2 and O2, at the same temperature, therefore must have the same
average kinetic energy. This can be represented by the following equation.

This equation can be simplified by multiplying both sides by two.

It can then be rearranged to give the following.

Taking the square root of both sides of this equation gives a relationship between the
ratio of the velocities at which the two gases move and the square root of the ratio of
their molecular weights.
 This equation is a modified form of Graham's law. It suggests that the velocity (or
rate) at which gas molecules move is inversely proportional to the square root of their
molecular weights.

Practice Problem 14:

Calculate the average velocity of an H2 molecule at 0 C if the average velocity of an O2

molecule at this temperature is 500 m/s.

Click here to check your answer to Practice Problem 14.

Click here to see a solution to Practice Problem 14.

The Kinetic Molecular Theory

While the ideal gas law deals with macroscopic quantities of gas, the kinetic
molecular theory shows how individual gas particles interact with one another.
The kinetic molecular theory contains a number of statements compatible with
the assumptions of the ideal gas law. It is worthwhile to list them here:

Molecules are point masses (they have no volume)

Gas molecules exert no force on each other unless they collide
Collisions of molecules with each other or the walls of the container do
not decrease the energy of the system
The molecules of a gas are in constant and random motion
The temperature of a gas depends on its average kinetic
energyavg(1/2mv 2) = 3/2kT . In other words, the energy of an ideal gas is
entirely kinetic.

The amazing thing about the kinetic molecular theory is that it can be used to
derive the ideal gas law. Such a derivation links the microscopic claims of the
kinetic molecular theory to the very visibly macroscopic behavior of the ideal
gas law. The derivation is beyond the scope of this note, but you should ask
your instructor to show you if you're interested.
Terms and Formulae
TERMS

Boltzmann constant - A constant, k , involved in the equation for average

velocity. k = 1.3810-23 J/K

Diffusion - Diffusion is the spread of one substance through another.

Effusion - Effusion is the rate at which a gas passes through a small hole
into a vacuum.

Kinetic energy - E k = 1/2mv 2

Kinetic molecular theory - A theory that models the interaction between

individual gas molecules. See the summary for more details.

Maxwell-Boltzmann speed distribution - The distibution attained when

molecule speed is set against the number of molecules sharing that speed.

Mean free path - The mean distance a molecule travels before it impacts
another molecule; given the huge number of collisions in a gas, the mean free
path is vastly smaller than any typical room or container. The equation for
mean free path:

m p - The most probable velocity at which the most molecules in a gas travel.
The formula for most probable velocity is:

v p = =
Root mean square velocity - An equation to measure the typical velocity of
molecules in a gas.

v rms =

FORMULAE

= =

Average velocity

2
Kinetic energy E k = 1/2mv

Mean free path

 v p = =

Formule for most probable

velocity

v =
rms

Formula for root mean square

velocity =

Gas Laws
One of the most amazing things about gases is that, despite
wide differences in chemical properties, all the gases more
or less obey the gas laws. The gas laws deal with how gases
behave with respect to pressure, volume, temperature, and
amount.
Pressure

Gases are the only state of matter that can be compressed

very tightly or expanded to fill a very large
space. Pressure is force per unit area, calculated by dividing
the force by the area on which the force acts. The earth's
gravity acts on air molecules to create a force, that of the air
pushing on the earth. This is called atmospheric pressure.

The units of pressure that are used are pascal (Pa), standard atmosphere (atm),
and torr. 1 atm is the average pressure at sea level. It is normally used as a
standard unit of pressure. The SI unit though, is the pascal. 101,325 pascals
equals 1 atm.
For laboratory work the atmosphere is very large. A more convient unit is the
torr. 760 torr equals 1 atm. A torr is the same unit as the mmHg (millimeter of
mercury). It is the pressure that is needed to raise a tube of mercury 1
millimeter.

The Gas Laws: Pressure Volume Temperature Relationships

Boyle's Law: The Pressure-Volume Law

Robert Boyle (1627-1691)

Boyle's law or the pressure-volume law states that the volume of a given amount
of gas held at constant temperature varies inversely with the applied pressure
when the temperature and mass are constant.

Another way to describing it is saying that their products are

constant.

PV = C

When pressure goes up, volume goes down. When volume goes up, pressure goes
down.
From the equation above, this can be derived:

P1V1 = P2V2 = P3V3 etc.

This equation states that the product of the initial volume and pressure is equal
to the product of the volume and pressure after a change in one of them under
constant temperature. For example, if the initial volume was 500 mL at a
pressure of 760 torr, when the volume is compressed to 450 mL, what is the
pressure?
Plug in the values:
P1V1 = P2V2

(760 torr)(500 mL) = P2(450 mL)

760 torr x 500 mL/450 mL = P2 844 torr = P2
The pressure is 844 torr after compression.

Charles' Law: The Temperature-Volume Law

Jacques Charles (1746 - 1823)

This law states that the volume of a given amount of gas held at constant
pressure is directly proportional to the Kelvin temperature.

V T

Same as before, a constant can be put in:

V/T=C

As the volume goes up, the temperature also goes up, and vice-versa.
Also same as before, initial and final volumes and temperatures under constant
pressure can be calculated.

V1 / T1 = V2 / T2 = V3 / T3 etc.

Gay-Lussac's Law: The Pressure Temperature Law

Joseph Gay-Lussac (1778-1850)

This law states that the pressure of a given amount of gas held at constant
volume is directly proportional to the Kelvin temperature.
P T

Same as before, a constant can be put in:

P/T=C

As the pressure goes up, the temperature also goes up, and vice-versa.
Also same as before, initial and final volumes and temperatures under constant
pressure can be calculated.

P1 / T1 = P2 / T2 = P3 / T3 etc.

Avogadro's Law: The Volume Amount Law

Amedeo Avogadro (1776-1856)

Gives the relationship between volume and amount when pressure and
temperature are held constant. Remember amount is measured in moles. Also,
since volume is one of the variables, that means the container holding the gas is
flexible in some way and can expand or contract.

If the amount of gas in a container is increased, the volume increases. If the

amount of gas in a container is decreased, the volume decreases.

V n

As before, a constant can be put in:

V/n=C

This means that the volume-amount fraction will always be the same value if the
pressure and temperature remain constant.

V1 / n1 = V2 / n2 = V3 / n3 etc.
The Combined Gas Law
Now we can combine everything we have into one
proportion:

The volume of a given amount of gas is proportional to the

ratio of its Kelvin temperature and its pressure.
Same as before, a constant can be put in:

PV / T = C

As the pressure goes up, the temperature also goes up, and vice-versa.
Also same as before, initial and final volumes and temperatures under constant
pressure can be calculated.

P1V1 / T1 = P2V2 / T2 = P3V3 / T3 etc.

The Ideal Gas Law

The previous laws all assume that the gas being measured is
an ideal gas, a gas that obeys them all exactly. But over a
wide range of temperature, pressure, and volume, real
gases deviate slightly from ideal. Since, according to
Avogadro, the same volumes of gas contain the same
number of moles, chemists could now determine the
formulas of gaseous elements and their formula masses.
The idea gas law is:

PV = nRT

Where n is the number of moles of the number of moles and R is a constant called
the universal gas constant and is equal to approximately 0.0821 L-atm / mole-K.

EXAMPLE 1:

The balloon used by Charles in his historic flight in 1783 was filled with about
1300 mole of H2. If the outside temperature was 21 oC and the atmospheric
pressure was 750 mm Hg, what was the volume of the balloon?

Quanti
Raw data Conversion Data with proper units
ty

P 750 mm Hg x 1 atm / 760 torr = 0.9868 atm

V ? ?

n 1300 mole H2 1300 mole H2

R 0.0821 L-atm / mole-K 0.0821 L-atm / mole-K

T 21 oC + 273 = 294 K

V = nRT / P ; V = (1300 mole)(0.0821 L-atm/mole-K)(294 K) / (0.9868 atm) =

31798.358 L = 3.2 x 104 L.

Other Forms of the Gas Law

If the definition of the mole is included in the equation, the

result is:

PV = gRT / FW

or

FW = gRT / PV

This equation provides a convenient way of determining the formula weight of a

gas if mass, temperature, volume and pressure of the gas are known (or can be
determined).

EXAMPLE 2:

A 0.1000 g sample of a compound with the empirical formula CHF2 is vaporized

into a 256 mL flask at a temperature of 22.3 oC. The pressure in the flask is
measured to be 70.5 torr. What is the molecular formula of the compound?
Quanti
Raw data Conversion Data with proper units
ty

P 70.5 torr x 1 atm / 760 torr = 0.0928 atm

V 256 mL x 1 L / 1000 mL = 0.256 L

g 0.1000 g sample 0.1000 g

R 0.0821 L-atm / mole-K 0.0821 L-atm / mole-K

T 22.3 oC + 273 = 295.3 K

FW ? ?

FW = gRT / PV ; V = (0.1000 g)(0.0821 L-atm / mole-K)(295.3 K) / (0.0928 atm)

(0.256 L) = 102 g / mole

FW of CHF2 = 51.0 g / mole ; 102 / 51.0 = 2 ; C2H2F4

If the equation above is rearranged further,

g / V = P x FW / RT = density

you get an expression of the density of the gas as a function of T and FW.

EXAMPLE 3:

Compare the density of He and air (average FW = 28 g/mole) at 25.0 oC and 1.00
atm.

dHe = (4.003 g / mole)(1.00 atm) / (0.0821 L-atm / mole-K)(298 K) = 0.164 g / L

dair = (28.0 g / mole)(1.00 atm) / (0.0821 L-atm / mole-K)(298 K) = 1.14 g / L

EXAMPLE 4:

Compare the density of air at 25.0 oC and air at 1807 oC and 1.00 atm.

dHe = (28.0 g / mole)(1.00 atm) / (0.0821 L-atm / mole-K)(298 K) = 1.14 g / L

dair = (28.0 g / mole)(1.00 atm) / (0.0821 L-atm / mole-K)(2080 K) = 0.164 g / L

Partial Pressures
 John Dalton (1766-1844)

Dalton's Law of Partial Pressures states that the total pressure of a mixture of
nonreacting gases is the sum of their individual partial pressures.

Ptotal = Pa + Pb + Pc + ...

or

Ptotal = naRT / V + nbRT / V + ncRT / V + ...

or

Ptotal = (na+ nb+ nc+ ... )RT / V

The pressure in a flask containing a mixture of 1 mole of 0.20 mole O 2 and 0.80
mole N2 would be the same as the same flask holding 1 mole of O 2.

Partial pressures are useful when gases are collected by bubbling through water
(displacement). The gas collected is saturated in water vapor which contibutes to
the total number of moles of gas in the container.

EXAMPLE 5:

A sample of H2 was prepared in the laboratory by the reaction:

Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)

456 mL of gas was collected at 22.0 oC. The total pressure in the flask was 742
torr. How many moles of H2 were collected? The vapor pressure of H2O at
22.0 oC is 19.8 torr.
Quanti Data with proper
Raw data Conversion
ty units

Ptotal 742 torr

PH O2 19.8 torr

742 torr - 19.8 torr = 722.2 x 1 atm / 760 torr

PH 2 0.9503 atm
torr =

V 456 mL x 1 L / 1000 mL = 0.456 L

n ? ?

0.0821 L-atm / mole-

R 0.0821 L-atm / mole-K
K

T 22 oC + 273 = 295 K

nH = PH V / RT ; nH = (0.9503 atm)(0.456 L) / (0.0821 L-atm / mole-K)(295 K)

2 2 2

= 0.0179 mole H2.

Non-Ideal Gases

Johannes Diderik van der Waals (1837-1923)

The ideal gas equation (PV=nRT) provides a valuable model of the relations
between volume, pressure, temperature and number of particles in a gas. As an
ideal model it serves as a reference for the behavior of real gases. The ideal gas
equation makes some simplifying assumptions which are obviously not quite
true. Real molecules do have volume and do attract each other. All gases depart
from ideal behavior under conditions of low temperature (when liquefaction
begins) and high pressure (molecules are more crowed so the volume of the
molecule becomes important). Refinements to the ideal gas equation can be
made to correct for these deviations.

In 1873 J. D. van der Waals proposed his equation, known as the van der Waals
equation. As there are attractive forces between molecules, the pressure is lower
than the ideal value. To account for this the pressure term is augmented by an
attractive force term a/V2. Likewise real molecules have a volume. The volume
of the molecules is represented by the term b. The term b is a function of a
spherical diameter d known as the van der Waals diameter. The van der Waals
equation for n moles of gas is:

The values for a and b, below, are determined empirically:

Molecule a (liters2-atm / mole2) b (liters / mole)

H2 0.2444 0.02661

O2 1.360 0.03183

N2 1.390 0.03913

CO2 3.592 0.04267

Cl2 6.493 0.05622

Ar 1.345 0.03219

Ne 0.2107 0.01709

He 0.03412 0.02370

This article outlines the historical development of the laws describing ideal gases. For a detailed
description of the ideal gas laws and their further development see ideal gas law.

The gas laws were developed at the end of the 18th century, when scientists began to realize that
relationships between the pressure, volume and temperature of a sample of gas could be obtained
which would hold to a good approximation for all gases. Gases behave in a similar way over a wide
variety of conditions because they all have molecules which are widely spaced, and the equation of
state for an ideal gas is derived from kinetic theory. The earlier gas laws are now considered as
special cases of the ideal gas equation, with one or more of the variables held constant.

Boyle's Law[edit]
Main article: Boyle's Law

In 1662 Robert Boyle studied the relationship between the volume and pressure of a gas at constant
temperature.He observed that volume of a given mass of a gas is inversely proportional to its
pressure provided the temperature remains constant. Boyle's Law, published in 1662, states that, at
constant temperature, the product of the pressure and volume of a given mass of an ideal gas in a
closed system is always constant. It can be verified experimentally using a pressure gauge and a
variable volume container. It can also be derived from the kinetic theory of gases: if a container, with
a fixed number of molecules inside, is reduced in volume, more molecules will strike a given area of
the sides of the container per unit time, causing a greater pressure.

As a mathematical equation, Boyle's Law is written as either:

, or
, or
where P is the pressure, and V is the volume of a gas, and k1 is the constant in this equation
(and is not the same as the proportionality constants in the other equations below).

The statement of Boyle 's law is as follows:

The volume of a given mass of a gas is inversely related to the pressure exerted on
it at a given temperature and given number of moles.

Charles' Law[edit]
Main article: Charles's Law

Charles's Law, or the law of volumes, was found in 1787 by Jacques Charles. It
states that, for a given mass of an ideal gas at constant pressure, the volume is
directly proportional to its absolute temperature, assuming in a closed system.

As a mathematical equation, Charles's Law is written as either:

, or
, or
where V is the volume of a gas, T is the absolute temperature and k2 is a proportionality
constant (which is not the same as the proportionality constants in the other equations in this
article).

Gay-Lussac's Law[edit]
Main article: Gay-Lussac's Law
 Gay-Lussac's Law, Amontons' Law or the Pressure Law, was found
by Joseph Louis Gay-Lussac in 1809. It states that, for a given
mass and constant volume of an ideal gas, the pressure exerted on
the sides of its container is directly proportional to its absolute
temperature.

As a mathematical equation, Gay-Lussac's Law is written as either:

, or
, or
where P is the pressure, T is the absolute temperature, and k is another proportionality
constant.

Avogadro's Law[edit]
Main article: Avogadro's Law

Avogadro's Law states that the volume occupied

by an ideal gas is directly proportional to the
number of molecules of the gas present in the
container. This gives rise to the molar volume of a
gas, which at STP (273.15 K, 1 atm) is about
22.4 L. The relation is given by

where n is equal to the number of molecules of gas (or the number of moles of gas).

Combined and Ideal Gas

Laws[edit]
Main article: Ideal Gas Law

The Combined Gas Law or General Gas

Equation is obtained by combining Boyle's
Law, Charles' Law, and Gay-Lussac's Law.
It shows the relationship between the
pressure, volume, and temperature for a
fixed mass (quantity) of gas:

This can also be written as:

With the addition of Avogadro's

Law, the combined gas
law develops into the Ideal Gas
Law:

where
P is pressure
 V is volume
n is the number of moles
R is the universal gas constant
T is temperature (K)
where the proportionality constant, now named R, is the universal gas constant with a value
of 8.3144598 (kPaL)/(molK). An equivalent formulation of this Law is:
where
P is the pressure
V is the volume
N is the number of gas molecules
k is the Boltzmann constant (1.3811023 JK1 in SI units)
T is the absolute temperature

These equations are exact only for an ideal gas, which neglects various intermolecular effects
(see real gas). However, the ideal gas law is a good approximation for most gases under moderate
pressure and temperature.
This law has the following important consequences:

1. If temperature and pressure are kept constant, then the volume of the gas is directly
proportional to the number of molecules of gas.

2. If the temperature and volume remain constant, then the pressure of the gas changes is
directly proportional to the number of molecules of gas present.

3. If the number of gas molecules and the temperature remain constant, then the pressure is
inversely proportional to the volume.

4. If the temperature changes and the number of gas molecules are kept constant, then either
pressure or volume (or both) will change in direct proportion to the temperature.

Graham's law states that the rate at which gas molecules diffuse is inversely proportional to
the square root of its density. Combined with Avogadro's law (i.e. since equal volumes have
equal number of molecules) this is the same as being inversely proportional to the root of the
molecular weight.

Dalton's law of partial pressures states that the pressure of a mixture of gases simply is the
sum of the partial pressures of the individual components. Dalton's Law is as follows:
,
or
where PTotal is the total pressure of the atmosphere,
PGas is the pressure of the gas mixture in the atmosphere,
and PH O is the water pressure at that temperature.
2
 Henry's law states that:
At constant temperature, the amount of a given gas dissolved in a given type and volume of
liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.

Real gas law, formulated by Johannes Diderik van der

Waals (1873).

Early scientists explored the relationships among the pressure of a gas ( P) and its
temperature (T), volume (V), and amount (n) by holding two of the four variables
constant (amount and temperature, for example), varying a third (such as pressure),
and measuring the effect of the change on the fourth (in this case, volume). The history
of their discoveries provides several excellent examples of the scientific method.

The Relationship between Pressure and

Volume: Boyle's Law
As the pressure on a gas increases, the volume of the gas decreases because the gas
particles are forced closer together. Conversely, as the pressure on a gas decreases,
the gas volume increases because the gas particles can now move farther apart.
Weather balloons get larger as they rise through the atmosphere to regions of lower
pressure because the volume of the gas has increased; that is, the atmospheric gas
exerts less pressure on the surface of the balloon, so the interior gas expands until the
internal and external pressures are equal.

The Irish chemist Robert Boyle (16271691) carried out some of the earliest
experiments that determined the quantitative relationship between the pressure and the
volume of a gas. Boyle used a J-shaped tube partially filled with mercury, as shown in
Figure 6.2.1. In these experiments, a small amount of a gas or air is trapped above the
mercury column, and its volume is measured at atmospheric pressure and constant
temperature. More mercury is then poured into the open arm to increase the pressure
on the gas sample. The pressure on the gas is atmospheric pressure plus the difference
in the heights of the mercury columns, and the resulting volume is measured. This
process is repeated until either there is no more room in the open arm or the volume of
the gas is too small to be measured accurately. Data such as those from one of Boyles
own experiments may be plotted in several ways (Figure 6.2.2). A simple plot
of VV versus PP gives a curve called a hyperbola and reveals an inverse relationship
between pressure and volume: as the pressure is doubled, the volume decreases by a
factor of two. This relationship between the two quantities is described as follows:

PV=constant(6.2.1)(6.2.1)PV=constant
Figure 6.2.1: Boyles Experiment Using a J-Shaped Tube to Determine the Relationship
between Gas Pressure and Volume. (a) Initially the gas is at a pressure of 1 atm = 760
mmHg (the mercury is at the same height in both the arm containing the sample and
the arm open to the atmosphere); its volume is V. (b) If enough mercury is added to the
right side to give a difference in height of 760 mmHg between the two arms, the
pressure of the gas is 760 mmHg (atmospheric pressure) + 760 mmHg = 1520 mmHg
and the volume is V/2. (c) If an additional 760 mmHg is added to the column on the
right, the total pressure on the gas increases to 2280 mmHg, and the volume of the gas
decreases to V/3.

Dividing both sides by PP gives an equation illustrating the inverse relationship

between PP and VV:

V=const.P=const.(1P)(6.2.2)(6.2.2)V=const.P=const.(1P)

or

V1P(6.2.3)(6.2.3)V1P

where the symbol is read is proportional to. A plot of V versus 1/P is thus a straight
line whose slope is equal to the constant in Equation 6.2.1 and Equation 6.2.3. Dividing
both sides of Equation 6.2.1 by V instead of P gives a similar relationship
between P and 1/V. The numerical value of the constant depends on the amount of gas
used in the experiment and on the temperature at which the experiments are carried
out. This relationship between pressure and volume is known as Boyles law, after its
discoverer, and can be stated as follows: At constant temperature, the volume of a fixed
amount of a gas is inversely proportional to its pressure.

Figure 6.2.2: Plots of Boyles Data. (a) Here are actual data from a typical experiment
conducted by Boyle. Boyle used non-SI units to measure the volume (in. 3 rather than
cm3) and the pressure (in. Hg rather than mmHg). (b) This plot of pressure versus
volume is a hyperbola. Because PV is a constant, decreasing the pressure by a factor
of two results in a twofold increase in volume and vice versa. (c) A plot of volume versus
1/pressure for the same data shows the inverse linear relationship between the two
quantities, as expressed by the equation V = constant/P.

The Relationship between Temperature and

Volume: Charles's Law
Hot air rises, which is why hot-air balloons ascend through the atmosphere and why
warm air collects near the ceiling and cooler air collects at ground level. Because of this
behavior, heating registers are placed on or near the floor, and vents for air-conditioning
are placed on or near the ceiling. The fundamental reason for this behavior is that gases
expand when they are heated. Because the same amount of substance now occupies a
greater volume, hot air is less dense than cold air. The substance with the lower density
in this case hot airrises through the substance with the higher density, the cooler
air.

The first experiments to quantify the relationship between the temperature and the
volume of a gas were carried out in 1783 by an avid balloonist, the French chemist
Jacques Alexandre Csar Charles (17461823). Charless initial experiments showed
that a plot of the volume of a given sample of gas versus temperature (in degrees
Celsius) at constant pressure is a straight line. Similar but more precise studies were
carried out by another balloon enthusiast, the Frenchman Joseph-Louis Gay-Lussac
(17781850), who showed that a plot of V versus T was a straight line that could be
extrapolated to a point at zero volume, a theoretical condition now known to correspond
to 273.15C (Figure 6.2.3).A sample of gas cannot really have a volume of zero
because any sample of matter must have some volume. Furthermore, at 1 atm pressure
all gases liquefy at temperatures well above 273.15C. Note from part (a) in Figure
6.2.3 that the slope of the plot of V versus T varies for the same gas at different
pressures but that the intercept remains constant at 273.15C. Similarly, as shown in
part (b) in Figure 6.2.3, plots of V versus T for different amounts of varied gases are
straight lines with different slopes but the same intercept on the T axis.

Figure 6.2.3: The Relationship between Volume and Temperature. (a) In these plots of
volume versus temperature for equal-sized samples of H2 at three different pressures,
the solid lines show the experimentally measured data down to 100C, and the broken
lines show the extrapolation of the data to V = 0. The temperature scale is given in both
degrees Celsius and kelvins. Although the slopes of the lines decrease with increasing
pressure, all of the lines extrapolate to the same temperature at V = 0 (273.15C = 0
K). (b) In these plots of volume versus temperature for different amounts of selected
gases at 1 atm pressure, all the plots extrapolate to a value of V = 0 at 273.15C,
regardless of the identity or the amount of the gas.

The significance of the invariant T intercept in plots of V versus T was recognized in

1848 by the British physicist William Thomson (18241907), later named Lord Kelvin.
He postulated that 273.15C was the lowest possible temperature that could
theoretically be achieved, for which he coined the term absolute zero (0 K).

We can state Charless and Gay-Lussacs findings in simple terms: At constant

pressure, the volume of a fixed amount of gas is directly proportional to its absolute
temperature (in kelvins). This relationship, illustrated in part (b) in Figure 6.2.3 is often
referred to as Charless law and is stated mathematically as

V=const.T(6.2.4)(6.2.4)V=const.T

or

VT(6.2.5)(6.2.5)VT

with temperature expressed in kelvins, not in degrees Celsius. Charless law is valid for
virtually all gases at temperatures well above their boiling points.

The Relationship between Amount and

Volume: Avogadro's Law
We can demonstrate the relationship between the volume and the amount of a gas by
filling a balloon; as we add more gas, the balloon gets larger. The specific quantitative
relationship was discovered by the Italian chemist Amedeo Avogadro, who recognized
the importance of Gay-Lussacs work on combining volumes of gases. In 1811,
Avogadro postulated that, at the same temperature and pressure, equal volumes of
gases contain the same number of gaseous particles (Figure 6.2.4). This is the historic
Avogadros hypothesis.
Figure 6.2.4: Avogadros Hypothesis. Equal volumes of four different gases at the same
temperature and pressure contain the same number of gaseous particles. Because the
molar mass of each gas is different, the mass of each gas sample is different even
though all contain 1 mol of gas.

A logical corollary to Avogadro's hypothesis (sometimes called Avogadros law)

describes the relationship between the volume and the amount of a gas: At constant
temperature and pressure, the volume of a sample of gas is directly proportional to the
number of moles of gas in the sample. Stated mathematically,

V=const.(n)(6.2.6)(6.2.6)V=const.(n)

or

V.n@ constant T and P(6.2.7)(6.2.7)V.n@ constant T and P

This relationship is valid for most gases at relatively low pressures, but deviations from
strict linearity are observed at elevated pressures.

Note
For a sample of gas,

V increases as P decreases (and vice versa)

V increases as T increases (and vice versa)
V increases as n increases (and vice versa)

The relationships among the volume of a gas and its pressure, temperature, and
amount are summarized in Figure 6.2.5. Volume increases with increasing temperature
or amount but decreases with increasing pressure.
 Figure 6.2.5: The Empirically Determined Relationships among Pressure, Volume,
Temperature, and Amount of a Gas. The thermometer and pressure gauge indicate the
temperature and the pressure qualitatively, the level in the flask indicates the volume,
and the number of particles in each flask indicates relative amounts.

Summary
The volume of a gas is inversely proportional to its pressure and directly proportional to
its temperature and the amount of gas. Boyle showed that the volume of a sample of a
gas is inversely proportional to its pressure (Boyles law), Charles and Gay-Lussac
demonstrated that the volume of a gas is directly proportional to its temperature (in
kelvins) at constant pressure (Charless law), and Avogadro postulated that the volume
of a gas is directly proportional to the number of moles of gas present (Avogadros
law). Plots of the volume of gases versus temperature extrapolate to zero volume at
273.15C, which is absolute zero (0 K), the lowest temperature possible. Charless
law implies that the volume of a gas is directly proportional to its absolute temperature.

Gas Laws
Boyle's Law Amonton's Law Charles' Law Gay-Lussac's Law
Avogadro's The Ideal Gas Ideal Gas Dalton's Law of
Hypothesis Equation Calculations Partial Pressures
 Boyle's Law

Torricelli's experiment did more than just show that air has weight; it also provided a way of
creating a vacuum because the space above the column of mercury at the top of a barometer is
almost completely empty. (It is free of air or other gases except a negligible amount of mercury
vapor.) Torricelli's work with a vacuum soon caught the eye of the British scientist Robert Boyle.

Boyle's most famous experiments with gases dealt with what he called the "spring of air." These
experiments were based on the observation that gases are elastic. (They return to their original
size and shape after being stretched or squeezed.) Boyle studied the elasticity of gases in a J-
tube similar to the apparatus shown in the figure below. By adding mercury to the open end of
the tube, he trapped a small volume of air in the sealed end.

Boyle studied what happened to the volume of the gas in the sealed end of the tube as he added
mercury to the open end.

Boyle noticed that the product of the pressure times the volume for any measurement in this
table was equal to the product of the pressure times the volume for any other measurement,
within experimental error.

P1V1 = P2V2

This expression, or its equivalent,

is now known as Boyle's Law.

Practice Problem 3:

Calculate the pressure in atmospheres in a motorcycle engine at the end of the

compression stroke. Assume that at the start of the stroke, the pressure of the
mixture of gasoline and air in the cylinder is 745.8 mm Hg and the volume of each
cylinder is 246.8 mL. Assume that the volume of the cylinder is 24.2 mL at the
end of the compression stroke.

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Amonton's Law

Toward the end of the 1600s, the French physicist Guillaume Amontons built a thermometer
based on the fact that the pressure of a gas is directly proportional to its temperature. The
relationship between the pressure and the temperature of a gas is therefore known
as Amontons' law.

P T

Amontons' law explains why car manufacturers recommend adjusting the pressure of your tires
before you start on a trip. The flexing of the tire as you drive inevitably raises the temperature of
the air in the tire. When this happens, the pressure of the gas inside the tires increases.

Amontons' law can be demonstrated with the apparatus shown in the figure below, which
consists of a pressure gauge connected to a metal sphere of constant volume, which is immersed
in solutions that have different temperatures.

The apparatus for demonstrating Amonton's law consists of .

The following data were obtained with this apparatus.

In 1779 Joseph Lambert proposed a definition for absolute zero on the temperature scale that
was based on the straight-line relationship between the temperature and pressure of a gas
shown in the figure above.

He defined absolute zero as the temperature at which the pressure of a gas becomes zero
when a plot of pressure versus temperature for a gas is extrapolated. The pressure of a gas
approaches zero when the temperature is about -270C. When more accurate measurements are
made, the pressure of a gas extrapolates to zero when the temperature is -273.15C. Absolute
zero on the Celsius scale is therefore -273.15C.

The relationship between temperature and pressure can be greatly simplified by converting the
temperatures from the Celsius to the Kelvin scale.

TK = ToC + 273.15

When this is done, a plot of the temperature versus the pressure of a gas gives a straight line
that passes through the origin. Any two points along the line therefore fit the following equation.

It is important to remember that this equation is only valid if the temperatures are converted
from the Celsius to the Kelvin scale before calculations are done.

Practice Problem 4:

Assume that the pressure in the tires of your car is 32 lb/in 2 at 20C. What is the
pressure when the gas in these tires heats up to a temperature of 40C?

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 Charles' Law

On 5 June 1783, Joseph and Etienne Montgolfier used a fire to inflate a spherical balloon about
30 feet in diameter that traveled about a mile and one-half before it came back to earth. News of
this remarkable achievement spread throughout France, and Jacques-Alexandre-Cesar Charles
immediately tried to duplicate this performance. As a result of his work with balloons, Charles
noticed that the volume of a gas is directly proportional to its temperature.

V T

This relationship between the temperature and volume of a gas, which became known
as Charles' law, provides an explanation of how hot-air balloons work. Ever since the third
century B.C., it has been known that an object floats when it weighs less than the fluid it
displaces. If a gas expands when heated, then a given weight of hot air occupies a larger volume
than the same weight of cold air. Hot air is therefore less dense than cold air. Once the air in a
balloon gets hot enough, the net weight of the balloon plus this hot air is less than the weight of
an equivalent volume of cold air, and the balloon starts to rise. When the gas in the balloon is
allowed to cool, the balloon returns to the ground.

Charles' law can be demonstrated with the apparatus shown in the figure below. A 30-mL syringe
and a thermometer are inserted through a rubber stopper into a flask that has been cooled to
0C. The ice bath is then removed and the flask is immersed in a warm-water bath. The gas in the
flask expands as it warms, slowly pushing the piston out of the syringe. The total volume of the
gas in the system is equal to the volume of the flask plus the volume of the syringe.
The figure below shows a plot of the typical data obtained from this experiment.

This graph provides us with another way of defining absolute zero on the temperature
scale. Absolute zero is the temperature at which the volume of a gas becomes zero when the a
plot of the volume versus temperature for a gas are extrapolated. As expected, the value of
absolute zero obtained by extrapolating the data is essentially the same as the value obtained
from the graph of pressure versus temperature in the preceding section. Absolute zero can
therefore be more accurately defined as the temperature at which the pressure and the volume
of a gas extrapolate to zero.

A plot of the volume versus the temperature of a gas (when the temperatures obtained are
converted from Celsius to the Kelvin scale) becomes a straight line that passes through the
origin. Any two points along this line can therefore be used to construct the following equation,
which is known as Charles' law.

Before using this equation, it is important to remember that temperatures must be converted
from C to K.

Practice Problem 5:

Assume that the volume of a balloon filled with H2 is 1.00 L at 25C. Calculate the
volume of the balloon when it is cooled to -78C in a low-temperature bath made
by adding dry ice to acetone.

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Gay-Lussac's Law

Joseph Louis Gay-Lussac (1778-1850) began his career in 1801 by very carefully showing the
validity of Charles' law for a number of different gases. Gay-Lussac's most important
contributions to the study of gases, however, were experiments he performed on the ratio of the
volumes of gases involved in a chemical reaction.

Gay-Lussac studied the volume of gases consumed or produced in a chemical reaction because
he was interested in the reaction between hydrogen and oxygen to form water. He argued that
measurements of the weights of hydrogen and oxygen consumed in this reaction could be
influenced by the moisture present in the reaction flask, but this moisture would not affect
the volumes of hydrogen and oxygen gases consumed in the reaction.

Much to his surprise, Gay-Lussac found that 199.89 parts by volume of hydrogen were consumed
for every 100 parts by volume of oxygen. Thus, hydrogen and oxygen seemed to combine in a
simple 2:1 ratio by volume.

hydrogen + oxygen water

2 volumes 1 volume
Gay-Lussac found similar whole-number ratios for the reaction between other pairs of gases. The
compound we now know as hydrogen chloride (HCl) combined with ammonia (NH3) in a simple
1:1 ratio by volume:

hydrogen chloride + ammonia ammonium chloride

1 volume 1 volume

Carbon monoxide combined with oxygen in a 2:1 ratio by volume:

carbon monoxide + oxygen carbon dioxide

2 volumes 1 volume

Gay-Lussac obtained similar results when he analyzed the volumes of gases given off when
compounds decomposed. Ammonia, for example, decomposed to give three times as much
hydrogen by volume as nitrogen:

ammonia nitrogen + hydrogen

1 volume 3 volumes

On 31 December 1808, Gay-Lussac announced his law of combining volumes to a meeting of

the Societ Philomatique in Paris. At that time, he summarized the law as follows: Gases combine
among themselves in very simple proportions. Today, Gay-Lussac's law is stated as follows: The
ratio of the volumes of gases consumed or produced in a chemical reaction is equal to
the ratio of simple whole numbers.

Practice Problem 6:

Use the following balanced chemical equations to explain the results of Gay-
Lussac's experiments:

2 H2(g) + O2(g) 2H2O(g)

HCl(g) + NH3(g) NH4Cl(s)

2 CO(g) + O2(g) 2 CO2(g)

2 NH3(g) N2 + 3 H2(g)

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Avogadro's Hypothesis
Gay-Lussac's law of combining volumes was announced only a few years after John Dalton
proposed his atomic theory. The link between these two ideas was first recognized by the Italian
physicist Amadeo Avogadro three years later, in 1811. Avogadro argued that Gay-Lussac's law of
combining volumes could be explained by assuming that equal volumes of different gases
collected under similar conditions contain the same number of particles.

HCl and NH3 therefore combine in a 1:1 ratio by volume because one molecule of HCl is
consumed for every molecule of NH3in this reaction and equal volumes of these gases contain the
same number of molecules.

NH3(g) + HCl(g) NH4Cl(s)

Anyone who has blown up a balloon should accept the notion that the volume of a gas is
proportional to the number of particles in the gas.

V n

The more air you add to a balloon, the bigger it gets. Unfortunately this example does not
test Avogadro's hypothesis that equal volumes of different gases contain the same number of
particles. The best way to probe the validity of this hypothesis is to measure the number of
molecules in a given volume of different gases, which can be done with the apparatus shown in
the figure below.

A small hole is drilled through the plunger of a 50-mL plastic syringe. The plunger is then pushed
into the syringe and the syringe is sealed with a syringe cap. The plunger is then pulled out of
the syringe until the volume reads 50 mL and a nail is inserted through the hole in the plunger so
that the plunger is not sucked back into the barrel of the syringe. The "empty" syringe is then
weighed, the syringe is filled with 50 mL of a gas, and the syringe is reweighed. The difference
between these measurements is the mass of 50 mL of the gas.

The results of experiments with six gases are given in the table below.

Experimental Data for the Mass of 50-mL Samples of Different Gases

Mass of Molecular Number of

Compound 50 mL of Gas (g) Weight of Gas Gas Molecules
H2 0.005 2.02 1 x 1021
N2 0.055 28.01 1.2 x 1021
O2 0.061 32.00 1.1 x 1021
CO2 0.088 44.01 1.2 x 1021
C4H10 0.111 58.12 1.15 x 1021
CCl2F2 0.228 120.91 1.14 x 1021

The number of molecules in a 50-mL sample of any one of these gases can be calculated from
the mass of the sample, the molecular weight of the gas, and the number of molecules in a
mole. Consider the following calculation of the number of H2molecules in 50 mL of hydrogen gas,
for example.

The last column in the table above summarizes the results obtained when this calculation is
repeated for each gas. The number of significant figures in the answer changes from one
calculation to the next. But the number of molecules in each sample is the same, within
experimental error. We therefore conclude that equal volumes of different gases collected under
the same conditions of temperature and pressure do in fact contain the same number of
particles.

The Ideal Gas Equation

Gases can described in terms of four variables: pressure (P), volume (V), temperature (T), and
the amount of gas (n). There are five relationships between pairs of these variables in which two
of the variables were allowed to cahnge while the other two were held constant.

P n (T and V constant)
Boyle's law: P 1/V (T and n constant)
Amontons' law: P T (V and n constant)
Charles' law: V T (P and n constant)
Avogadro's hypothesis: V n (P and T constant)

Each of these relationships is a special case of a more general relationship known as the ideal
gas equation.

PV = nRT

In this equation, R is a proportionality constant known as the ideal gas constant and T is the
absolute temperature. The value of R depends on the units used to express the four
variables P, V, n, and T. By convention, most chemists use the following set of units.

P: atmospheres
T: kelvin
V: liters
n: moles
Practice Problem 7:

Calculate the value of the ideal gas constant, R, if exactly 1 mole of an ideal gas
occupies a volume of 22.414 liters at 0C and 1 atmosphere pressure.

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Ideal Gas Calculations

The ideal gas equation can be used to predict the value of any one of the variables that describe
a gas from known values of the other three.

Practice Problem 8:

Many gases are available for use inthe laboratory in compressed gas cylinders, in
which they are stored at high pressures. Let's calculate the mass of O 2 that can be
stored at 21C and 170 atm in a cylinder with a volume of 60.0 L.

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The key to solving ideal gas problems often involves recognizing what is known and deciding how
to use this information.

Practice Problem 9:

Let's calculate the mass of the air in a hot-air balloon that has a volume of 4.00 x
105 liters when the temperature of the gas is 30C and the presure is 748 mmHg.
Let's assume the average molar mass of air is 29.0 grams per mole.

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The ideal gas equation can be applied to problems that don't seem to ask for one of the variables
in this equation.
Practice Problem 10:

Let's calculate the molecular weight of butane if 0.5813 gram of this gas fills a
250.0-mL flask at a temperature of 24.4C and a pressure of 742.6 mmHg.

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The ideal gas equation can even be used to solve problems that don't seem to contain enough
information.

Practice Problem 11:

Let's calculate the density in grams per liter of O2 gas at 0C and 1.00 atm.

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Gas law problems often ask you to predict what happens when one or more changes are made in
the variables that describe the gas. There are two ways of working these problems. A powerful
approach is based on the fact that the ideal gas constant is in fact a constant.

We start by solving the ideal gas equation for the ideal gas constant.

We then note that the ratio of PV/nT at any time must be equal to this ratio at any other time.

We then substitute the known values of pressure, temperature, volume, and amount of gas into
this equation and solve for the appropriate unknown. This approach has two advantages. First,
only one equation has to be remembered. Second, it can be used to handle problems in which
more than one variable changes at a time.
 Dalton's Law of Partial Pressures

The CRC Handbook of Chemistry and Physics describes the atmosphere as 78.084% N2, 20.946%
O2, 0.934% Ar, and 0.033% CO2 by volume when the water vapor has been removed. What
image does this description evoke in your mind? Do you believe that only 20.463% of the room
in which you are sitting contains O2? Or do you believe that the atmosphere in your room is a
more or less homogeneous mixture of these gases?

Gases expand to fill their containers. The volume of O2 in your room is therefore the same as the
volume of N2. (Both gases expand to fill the room.) When we describe the atmosphere as
20.946% O2 by volume, we mean that the volume of the atmosphere would shrink by 20.946% if
the O2 is removed.

What about the pressure of the different gases in your room? Is the pressure of the O 2 in the
atmosphere the same as the pressure of the N2? We can answer this question by rearranging the
ideal gas equation as follows.

According to this equation, the pressure of a gas is proportional to the number of moles of gas, if
the temperature and volume are held constant. Because the temperature and volume of the
O2 and N2 in the atmosphere are the same, the pressure of each gas must be proportional to the
number of the moles of the gas. Because there is more N2 in the atmosphere than O2, the
contribution to the total pressure of the atmosphere from N2 is larger than the contribution from
O 2.

John Dalton was the first to recognize that the total pressure of a mixture of gases is the sum of
the contributions of the individual components of the mixture. By convention, the part of the
total pressure of a mixture that results from one component is called the partial pressure of
that component. Dalton's law of partial pressures states that the total pressure of a mixture
of gases is the sum of the partial pressures of the various components.

PT = P1 + P2 + P3 + ...

Practice Problem 12:

Calculate the total pressure of a mixture that contains 1.00 g H2 and 1.00 g of He
in a 5.00 L container at 21 C.

Click here to check your answer to Practice Problem 12.

Click here to see a solution to Practice Problem 12.

Dalton derived the law of partial pressures from his work on the amount of water vapor that
could be absorbed by air at different temperatures. It is therefore fitting that this law is used
most often to correct for the amount of water vapor picked up when a gas is collected by
displacing water. Suppose, for example, that we want to collect a sample of O2 prepared by
heating potassium chlorate until it decomposes.
2 KClO3(s) 2 KCl(s) + 3 O2(g)

The gas given off in this reaction can be collected by filling a flask with water, inverting the flask
in a trough, and then letting the gas bubble into the flask as shown in the figure below.

Because some of the water in the flask will evaporate during the experiment, the gas that
collects in this flask is going to be a mixture of O2 and water vapor. The total pressure of this gas
is the sum of the partial pressures of these two components.

PT = Poxygen + Pwater

The total pressure of this mixture must be equal to atmospheric pressure. (If it was any greater,
the gas would push water out of the container. If it was any less, water would be forced into the
container.) If we had some way to estimate the partial pressure of the water in this system, we
could therefore calculate the partial pressure of the oxygen gas.

By convention, the partial pressure of the gas that collects in a closed container above a liquid is
known as the vapor pressure of the liquid. If we know the temperature at which a gas is
collected by displacing water, and we assume that the gas is saturated with water vapor
at this temperature, we can calculate the partial pressure of the gas by subtracting
the vapor pressure of water from the total pressure of the mixture of gases collected
in the experiment.

10.3 Relationships among Pressure, Temperature, Volume, and

Amount

L EA RNI NG OBJE CT IV E

1. To understand the relationships among pressure, temperature, volume,

and the amount of a gas.

Early scientists explored the relationships among the pressure of a gas (P) and its temperature (T),

volume (V), and amount (n) by holding two of the four variables constant (amount and temperature,

for example), varying a third (such as pressure), and measuring the effect of the change on the fourth

(in this case, volume). The history of their discoveries provides several excellent examples of the

scientific method as presented in Chapter 1 "Introduction to Chemistry".

The Relationship between Pressure and Volume

As the pressure on a gas increases, the volume of the gas decreases because the gas
particles are forced closer together. Conversely, as the pressure on a gas decreases, the
gas volume increases because the gas particles can now move farther apart. Weather
balloons get larger as they rise through the atmosphere to regions of lower pressure
because the volume of the gas has increased; that is, the atmospheric gas exerts less
pressure on the surface of the balloon, so the interior gas expands until the internal and
external pressures are equal.

Robert Boyle (16271691)

Boyle, the youngest (and 14th!) child of the Earl of Cork, was an important early figure
in chemistry whose views were often at odds with accepted wisdom. Boyles studies of
gases are reported to have utilized a very tall J-tube that he set up in the entryway of his
house, which was several stories tall. He is known for the gas law that bears his name
and for his book, The Sceptical Chymist, which was published in 1661 and influenced
chemists for many years after his death. In addition, one of Boyles early essays on
morals is said to have inspired Jonathan Swift to write Gullivers Travels.

The Irish chemist Robert Boyle (16271691) carried out some of the earliest experiments
that determined the quantitative relationship between the pressure and the volume of a
gas. Boyle used a J-shaped tube partially filled with mercury, as shown in Figure 10.6
"Boyles Experiment Using a J-Shaped Tube to Determine the Relationship between Gas
Pressure and Volume". In these experiments, a small amount of a gas or air is trapped
above the mercury column, and its volume is measured at atmospheric pressure and
constant temperature. More mercury is then poured into the open arm to increase the
pressure on the gas sample. The pressure on the gas is atmospheric pressure plus the
difference in the heights of the mercury columns, and the resulting volume is measured.
This process is repeated until either there is no more room in the open arm or the
volume of the gas is too small to be measured accurately. Data such as those from one of
Boyles own experiments may be plotted in several ways (Figure 10.7 "Plots of Boyles
Data"). A simple plot of V versus P gives a curve called a hyperbola and reveals
an inverse relationship between pressure and volume: as the pressure is doubled, the
volume decreases by a factor of two. This relationship between the two quantities is
described as follows:

Equation 10.5

PV = constant

Figure 10.6 Boyles Experiment Using a J-Shaped Tube to Determine the Relationship between

Gas Pressure and Volume

(a) Initially the gas is at a pressure of 1 atm = 760 mmHg (the mercury is at the same height in
both the arm containing the sample and the arm open to the atmosphere); its volume is V. (b)

If enough mercury is added to the right side to give a difference in height of 760 mmHg
between the two arms, the pressure of the gas is 760 mmHg (atmospheric pressure) + 760

mmHg = 1520 mmHg and the volume is V/2. (c) If an additional 760 mmHg is added to the
column on the right, the total pressure on the gas increases to 2280 mmHg, and the volume of

the gas decreases to V/3.

Figure 10.7 Plots of Boyles Data

(a) Here are actual data from a typical experiment conducted by Boyle. Boyle used non-SI
units to measure the volume (in.3 rather than cm3) and the pressure (in. Hg rather than

mmHg). (b) This plot of pressure versus volume is a hyperbola. Because PV is a constant,
decreasing the pressure by a factor of two results in a twofold increase in volume and vice

versa. (c) A plot of volume versus 1/pressure for the same data shows the inverse linear
relationship between the two quantities, as expressed by the equation V = constant/P.

Dividing both sides by P gives an equation illustrating the inverse relationship

between P and V:

Equation 10.6

V=constantP=constant(1P) or V1P

where the symbol is read is proportional to. A plot of V versus 1/P is thus a straight
line whose slope is equal to the constant in Equation 10.5 and Equation 10.6. Dividing
both sides of Equation 10.5 by V instead of P gives a similar relationship between P and
1/V. The numerical value of the constant depends on the amount of gas used in the
experiment and on the temperature at which the experiments are carried out. This
relationship between pressure and volume is known as Boyles law, after its discoverer,
and can be stated as follows: At constant temperature, the volume of a fixed amount of
a gas is inversely proportional to its pressure.

The Relationship between Temperature and Volume

Hot air rises, which is why hot-air balloons ascend through the atmosphere and why
warm air collects near the ceiling and cooler air collects at ground level. Because of this
behavior, heating registers are placed on or near the floor, and vents for air-conditioning
are placed on or near the ceiling. The fundamental reason for this behavior is that gases
expand when they are heated. Because the same amount of substance now occupies a
greater volume, hot air is less dense than cold air. The substance with the lower density
in this case hot airrises through the substance with the higher density, the cooler air.

The first experiments to quantify the relationship between the temperature and the
volume of a gas were carried out in 1783 by an avid balloonist, the French chemist
Jacques Alexandre Csar Charles (17461823). Charless initial experiments showed
that a plot of the volume of a given sample of gas versus temperature (in degrees
Celsius) at constant pressure is a straight line. Similar but more precise studies were
carried out by another balloon enthusiast, the Frenchman Joseph-Louis Gay-Lussac
(17781850), who showed that a plot of V versus T was a straight line that could be
extrapolated to a point at zero volume, a theoretical condition now known to correspond
to 273.15C (Figure 10.8 "The Relationship between Volume and Temperature").A
sample of gas cannot really have a volume of zero because any sample of matter must
have some volume. Furthermore, at 1 atm pressure all gases liquefy at temperatures well
above 273.15C. Note from part (a) in Figure 10.8 "The Relationship between Volume
and Temperature" that the slope of the plot of V versus T varies for the same gas at
different pressures but that the intercept remains constant at 273.15C. Similarly, as
shown in part (b) in Figure 10.8 "The Relationship between Volume and Temperature",
plots of V versus T for different amounts of varied gases are straight lines with different
slopes but the same intercept on the T axis.

Jacques Alexandre Csar Charles (17461823) and

Joseph-Louis Gay-Lussac (17781850)

In 1783, Charles filled a balloon (aerostatic globe) with hydrogen (generated by the
reaction of iron with more than 200 kg of acid over several days) and flew successfully
for almost an hour. When the balloon descended in a nearby village, however, the
terrified townspeople destroyed it. In 1804, Gay-Lussac managed to ascend to 23,000 ft
(more than 7000 m) to collect samples of the atmosphere to analyze its composition as a
function of altitude. In the process, he had trouble breathing and nearly froze to death,
but he set an altitude record that endured for decades. (To put Gay-Lussacs
achievement in perspective, recall that modern jetliners cruise at only 35,000 ft!)

The significance of the invariant T intercept in plots of V versus T was recognized in

1848 by the British physicist William Thomson (18241907), later named Lord Kelvin.
He postulated that 273.15C was the lowest possible temperature that could
theoretically be achieved, for which he coined the term absolute zero (0 K).

We can state Charless and Gay-Lussacs findings in simple terms: At constant pressure,
the volume of a fixed amount of gas is directly proportional to its absolute
temperature (in kelvins). This relationship, illustrated in part (b) in Figure 10.8 "The
Relationship between Volume and Temperature", is often referred to as Charless
law and is stated mathematically as

Equation 10.7

V=(constant)[T(in K)] or VT(in K, at constant P)

Charless law is valid for virtually all gases at temperatures well above their boiling
points. Note that the temperature must be expressed in kelvins, not in degrees Celsius.

Figure 10.8 The Relationship between Volume and Temperature

(a) In these plots of volume versus temperature for equal-sized samples of H 2 at three different
pressures, the solid lines show the experimentally measured data down to 100C, and the

broken lines show the extrapolation of the data to V = 0. The temperature scale is given in both
degrees Celsius and kelvins. Although the slopes of the lines decrease with increasing pressure,

all of the lines extrapolate to the same temperature at V = 0 (273.15C = 0 K). (b) In these
plots of volume versus temperature for different amounts of selected gases at 1 atm pressure,

all the plots extrapolate to a value of V = 0 at 273.15C, regardless of the identity or the
amount of the gas.

The Relationship between Amount and Volume

We can demonstrate the relationship between the volume and the amount of a gas by
filling a balloon; as we add more gas, the balloon gets larger. The specific quantitative
relationship was discovered by the Italian chemist Amedeo Avogadro, who recognized
the importance of Gay-Lussacs work on combining volumes of gases. In 1811, Avogadro
postulated that, at the same temperature and pressure, equal volumes of gases contain
the same number of gaseous particles (Figure 10.9 "Avogadros Hypothesis"). (This is
the historic Avogadros hypothesis introduced in Chapter 1 "Introduction to
Chemistry".) A logical corollary, sometimes called Avogadros law, describes the
relationship between the volume and the amount of a gas: At constant temperature and
pressure, the volume of a sample of gas is directly proportional to the number of moles
of gas in the sample. Stated mathematically,

Equation 10.8

V=(constant)(n) or Vn (constant T and P)

This relationship is valid for most gases at relatively low pressures, but deviations from
strict linearity are observed at elevated pressures.

Note the Pattern

For a sample of gas,

V increases as P decreases (and vice versa)

V increases as T increases (and vice versa)

V increases as n increases (and vice versa)

Figure 10.9 Avogadros Hypothesis

Equal volumes of four different gases at the same temperature and pressure contain the same
number of gaseous particles. Because the molar mass of each gas is different, the mass of each

gas sample is different even though all contain 1 mol of gas.

The relationships among the volume of a gas and its pressure, temperature, and amount
are summarized in Figure 10.10 "The Empirically Determined Relationships among
Pressure, Volume, Temperature, and Amount of a Gas". Volume increases with
increasing temperature or amount but decreases with increasing pressure.

Figure 10.10 The Empirically Determined Relationships among Pressure, Volume,

Temperature, and Amount of a Gas
The thermometer and pressure gauge indicate the temperature and the pressure qualitatively,
the level in the flask indicates the volume, and the number of particles in each flask indicates

relative amounts.

Summary

Boyle showed that the volume of a sample of a gas is inversely proportional to its
pressure (Boyles law), Charles and Gay-Lussac demonstrated that the volume of a gas
is directly proportional to its temperature (in kelvins) at constant pressure (Charless
law), and Avogadro postulated that the volume of a gas is directly proportional to the
number of moles of gas present (Avogadros law). Plots of the volume of gases versus
temperature extrapolate to zero volume at 273.15C, which is absolute zero (0 K),
the lowest temperature possible. Charless law implies that the volume of a gas is
directly proportional to its absolute temperature.

KE Y TA KE AWAY

The volume of a gas is inversely proportional to its pressure and directly

proportional to its temperature and the amount of gas.

C ONCE PT U AL PROBL E MS

1. Sketch a graph of the volume of a gas versus the pressure on the gas.
What would the graph of V versus P look like if volume was directly
proportional to pressure?

2. What properties of a gas are described by Boyles law, Charless law,

and Avogadros law? In each law, what quantities are held constant? Why
does the constant in Boyles law depend on the amount of gas used and
the temperature at which the experiments are carried out?

3. Use Charless law to explain why cooler air sinks.

4. Use Boyles law to explain why it is dangerous to heat even a small
quantity of water in a sealed container.

A NSWE R
1.

2.

3.

4.

NU ME RIC AL PROBL E MS

1. A 1.00 mol sample of gas at 25C and 1.0 atm has an initial volume of
22.4 L. Calculate the results of each change, assuming all the other
conditions remain constant.

a. The pressure is changed to 85.7 mmHg. How many milliliters does the
gas occupy?

b. The volume is reduced to 275 mL. What is the pressure in millimeters

of mercury?

c. The pressure is increased to 25.3 atm. What is the temperature in

degrees Celsius?

d. The sample is heated to 30C. What is the volume in liters?

e. The sample is compressed to 1255 mL, and the pressure is increased

to 2555 torr. What is the temperature of the gas in kelvins?

2. A 1.00 mol sample of gas is at 300 K and 4.11 atm. What is the volume
of the gas under these conditions? The sample is compressed to 6.0 atm
at constant temperature, giving a volume of 3.99 L. Is this result
consistent with Boyles law?

A NSWE R

1.
a. 1.99 105 mL
b. 6.19 104 mmHg

c. 7270C
d. 22.8 L

e. 51.4 K

Pressure and temperature

relationship of a gas
The Pressure Law
The pressure law states:

"For a fixed mass of gas, at a constant volume, the

pressure (p) is directly proportional to the absolute
temperature (T)."

Pressure Temperature
Pressure
= constant
Temperature
A sealed cylinder with no leaks contains a fixed mass. The volume of the gas
is kept constant by using a cylinder with a fixed roof capable of withstanding
high pressures.The gas pressure is created by the collision of the moving gas
particles with each other and against the walls of the cylinder.

The following set up is used to investigate the relationship between

temperature and pressure for a gas. Heat energy is applied to the cylinder
and the temperature of the gas increases. The average velocity of the gas
particles increases resulting in an increase in the rate of collisions and the
average force per collision. Because the areas of the walls are kept constant,
the force per unit area increases resulting in an increase in pressure.

Plotting the pressure (p) against the absolute temperature (T) gives a
straight line which when extrapolated passes through the origin. This shows
the pressure of the gas is directly proportional to the absolute temperature of
the gas. Doubling the temperature will double the pressure for a fixed mass
of gas at constant volume. The gradient of the slope is the constant in
Charles Law. It also shows that if the gas is cooled to absolute zero then the
energy of the molecules is at the lowest energy state and therefore cannot
generate any pressure.

Pressure Law Example:

Using the example of the sealed cylinder above the pressure of gas is
recorded as 1.0 x 105 N/m2 at a temperature of 0C. The cylinder is heated
further till the thermometer records 150C. What is the pressure of the gas?

Solution:
We know

p/T = constant

therefore,

p1/T1 = p2/T2

p1 = 1.0 x 105 N/m2

T1 = 0C = 0+273 = 273K (remember to convert from Celsius to Kelvin)
T2 = 150C = 150+273 = 423K
p2 =?

p1/T1 = p2/T2

p1x T2
p2 =
T1

1.0 x 105 x 423

p2=
273

= 1.54 x 105 N/m2

PRESSURE/TEMPERATURE/
VOLUME RELATIONSHIPS IN
CHEMISTRY

RELATED BOOK

U Can: Chemistry I For Dummies

By John T. Moore, Chris Hren, Peter J. Mikulecky

Part of U Can: Chemistry I For Dummies Cheat Sheet

When youre looking at gas laws and how pressure, temperature, and
volume are related in Chemistry, remembering how they all interact
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way to remember their relationships without having to remember every
detail of Boyles law, Charless law, and Gay-Lussacs law. All you
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These
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