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THE GASEOUS STATE

Gases

The quantitative particle theory applied to gases (more properly

called the Kinetic Theory of Gases) has shown to be
extremely useful in Chemistry. One of the great things about it
is that it explains some of the phenomena that you encounter in
your everyday life. For example, have you ever inflated a pool
float until it was firm, thrown it into a cold pool, and then
wondered why the float then seemed like it was not fully
inflated? What determines the time it takes to smell the
perfume of a woman who walks past you? How do hot air balloons work? How can a
small barbeque tank hold enough propane to cook with all summer long?

Gases have special properties that liquids and solids don't have. The particles that
make up the gas are free to move about, and a gas will take up the size and shape of
its container. Knowing the volume of a gas tells you very little about the quantity of
matter, because any sample of gas will “fill” its container. Consider how different a gas
is from a solid. In a gas, the size of the sample has very little to do with the size of the
actual particles that make up the gas itself. Even in relatively dense gas samples, the
space in between the particles will be much larger than the particles themselves.
For that reason gases are very easily (squeezed) so they show high compressibility.

Ideal Gases

Ideal gases are just an idea; or better, a model to face the study of real gases.
Nevertheless, in a first approximation and for an incredible high number of situations,
the ideal gas approximation leads to excellent results.

In this ideal gas model, we treat the particles as point masses, or particles with mass
but no volume. Ideal gases differ from real gases in another important way. In real
gases, there will be an attraction between the particles in the gas as they come close to
each other and between them and the particles of the container. These attractions (that
are responsible for gases turning into liquids) are often minor and in this approach are
neglected (considered to be zero).

It is important to remember the differences between real gases and ideal gases but it is
also important to remember that real gases will act most like ideal gases at low
pressure and high temperature, when the gas sample is less dense.
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Pressure

Suppose you pull from the ends of a spring: it gets tense. If you
squeeze a sponge or stretch a rubber film they will also get tense.
Tension is the degree of stiffness or tightness shown by the object
because of the forces on it. Tensions are different in different
directions in solid materials. Tension is many times (when direction is
not important) called pressure. In liquids and gases tension is the
same in all directions and pressure is the usual term to name it.

Pressure and force are frequently mistaken but, although being closely related they are
not the same thing. Pressure and force are related in the same way as population and
population density. Generally speaking pressure is defined and calculated as the ratio
between force and area.

Forces applied on a small surface will create a stronger deformation and tension
(pressure). A relatively small force on a very small surface can produce a tremendous
pressure. That is why a sharp knife cuts or a thumbnail can be punched in a wooden
block. Can you explain why you can stand up on the snow if you have skis or snow
shoes but you will sink if you don’t wear them?

The unit of pressure is the Pascal (Pa) a very small unit. One Pascal is the pressure
produced by a one Newton force (the weight of 100 g of ham) distributed on a one
square metre.

Pressure in gases

How is the pressure at the walls of a container filled with a gas

originated? According to the particle theory, particles are constantly
moving at random until they crash against the walls of the container.
The pressure on them is due to the continuous tiny collisions of the
gas particles against the solid walls of the jar or bottle.

In Chemistry, pressure is often measured in kilopascals (kPa), millimetres of mercury

(mm of Hg, also called torr after Torricelli who created the first barometer), or
atmospheres (atm). For convenience sake, a standard atmospheric pressure has been set
760 torr = 1.00 atm.

Pressure is measured with barometers (the atmospheric

pressure) or manometers (pressure gauges for gases in
containers). The figures to the right show two different
classes of manometers.
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Mass, volume, pressure and temperature in gases

If we have a block of wood, we know that a second block of the

same class of wood that has the same volume as the first one, will
have the same mass of the first block too. But having two equal
volumes of the same gas does not necessarily mean their masses are
equal! That is because most of the gas is empty space and the same
container can accommodate lots of extra particles! Nevertheless
there will be a difference in both systems: the pressure of the gases
will not be the same because in case one of them has more particles
there will be more collisions against the walls of the container.

Furthermore, if the system (container) that has more particles and more pressure is
cooled down, the collisions of the particles against the walls will be fewer (the particles
move more slowly) and less energetic. Consequently, lowering the temperature will
lower the pressure too and finally we can be hoaxed again because both systems have
the same volume and now also the same pressure yet not the same mass!

In the case of gases, masses and volumes behave as in solids and liquids provided
the temperature and the pressure is kept constant. By keeping the pressure and the
temperature at constant values, chemists operate measuring volumes of gases instead of
masses which is, in these cases, rather tedious and inaccurate. There are simple laws
that relate all these variables for a gas: let’s go deeper into them.

Boyle’s law

Imagine a gas sample trapped in a cylinder which allows you to adjust the volume. It
can be a sealed syringe with a plunger (piston) that can be pressed down. As you push
the plunger into the syringe’s body notice how the changes in volume cause the pressure
to change. The smaller the volume, the higher the pressure will go. This change is not
arbitrary: although both volume and pressure change at the same time, their product
remains constant. Because of the relationship between the pressure and volume of a gas
sample at constant temperature, if you double the value of one, you divide the other
by two. If you make the volume 10 times smaller, the pressure will be 10 times greater.
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This relationship, called Boyle's Law, is summarized by the statement: If temperature

remains constant the volume of a fixed mass of gas is inversely proportional to its
pressure.

When two variables are inversely proportional, like pressure and volume in the
example above, the product of the two variables will always remain constant. The
formula that can be used to calculate the effects of pressure changes on the volume of a
gas at constant temperature is shown below:

P1V1 = P2V2 (If T is constant)

Charles’ and Gay-Lussac’s Laws

Charles's law, states that at constant pressure, the volume of a fixed mass of gas is
directly proportional to its Kelvin temperature. Gases expand as they are heated and
they contract when they are cooled. In other words, as the temperature of a sample of
gas at constant pressure increases, the volume increases. As the temperature goes
down, the volume decreases as well.

The mathematical expression for Charles's law is shown below:

V1/T1 = V2/T2 (If P is constant)

Gay-Lussac’s law is similar to Charles’s but involves changes in pressure as the gas is
heated at constant volume. It states that at constant volume, the pressure of a fixed
mass of gas is directly proportional to its Kelvin temperature.

P1/T1 = P2/T2 (If V is constant)

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Remember that Charles' and Gay-Lussac’s laws calculations must be done in the
Kelvin scale.

Graphs

The three laws studied can be represented graphically just like any other function. In
Boyle’s law, as P T = a constant (call it kB) we can write P = kB/V. The plot of the
function is one of the branches of a hyperbola. For the other two laws V/T and P/T are
constants kC and kGL and solving both for V and P results in V = kCT and P = kGLT

Isotherms isobars isochors

The Ideal Gas Equation (Combined Laws)

Suppose a gas is at temperature T1 and has certain pressure and volume. If we squeeze
it keeping the same temperature, the new values of V and P will be somewhere on the
same isotherm. If in a second step we keep the new pressure constant but heat the gas to
a new temperature (we move from the red to the blue isotherm (T3). Now the three
variables P, V and T have changed. But it can be shown with a little maths and knowing
that the laws hold for each case we can get to the so called “Gas equation”

The meaning of this equation is that no matter what happens to a gas, as long as its mass
(the number of particles) is constant the values of the three properties, P, V and T are
linked and cannot be all three changed arbitrarily.

Summing Up: The Particle Theory Explanation of the Ideal Gases Laws

The pressure of a gas is caused by the continuous knocking of its particles against the
walls of the container. If the gas is in a cubic container (just to make things easier) its
particles will take some time to knock against the opposite walls of it. Now if the
container is squeezed to half its length (the volume is halved), but the particles move at
the same speed, they will make two trips in the same time they needed to make just one.
Consequently, they will collide with the walls twice as much and the pressure will be
doubled. This is what Boyle’s law states!
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If the box instead of being squeezed is heated, the particles will move faster and will
rebound more frequently and more energetically against the container’s walls. That is
why pressure increases with temperature (Gay-Lussac’s law). Similar reasoning leads to
Charles’ law.

STP : Standard Temperature and Pressure

For convenience, standard temperature has been set at 273 Kelvin, which is equal to 0oC
and standard pressure at 1.00 atmospheres (760 torr). Standard temperature and pressure
is abbreviated as STP.

STP T = 273 K P = 1 atm

QUESTIONS AND PROBLEMS

1- A brick weighs 20 N. It is 5 cm high, 10 cm wide and 20 cm long.

a- Calculate the area of the three different surfaces (sides)
b- Calculate the pressures produced by the brick on a tight rubber
sheet when it rests on each of its three different surfaces
c- In which case the tension of the rubber sheet will be the greatest?

2- A mass of 3.2 mg of oxygen is kept in a closed syringe at 20 ºC. The volume of

this mass is 24 cm3 and the pressure of the system is 1 atm (760 torr). What happens
to the gas’ pressure if:
a- The temperature is raised with the plunger kept in place.
b- The plunger is pushed down without changing the temperature.
c- You allow part of the gas to escape.

3- For the same mass of oxygen as in problem (2) find the pressure inside the
syringe if (at the same temperature) the plunger is moved to allow a volume of
a- 36 cm3 b- 48 cm3 c- 12 cm3 d- 2,4 cm3

4- The same mass of oxygen is immersed in a water bath at 40 ºC. If the volume is
kept constant (the plunger in original position): will the pressure rise to 2 atm?
Why? If your answer is negative find the value of the new pressure

5- After a chemical process in a closed container, the pressure of the gases inside is
650 torr. If the admission valve is open: will the gases escape or will air enter the
container?

6- Is the pressure of the air inside an inflated balloon equal to the external
atmospheric pressure? Give reasons for your answer.

7- A bubble of air is released by a deep-sea diver at a depth where the pressure is 4

atm. Assuming that its temperature remains constant: how much bigger its volume
will be just before reaching the surface where the pressure is 1 atm.?
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8- The pressure of the air in a car tyres 2.7 atm when the temperature is -3 °C. If
the temperature rises to 27 °C what is the pressure then? Assume the volume doesn’t
change.)
9- A mass of gas has a volume of 380 cm 3 at a pressure of 560 torr and at a
temperature of 7 °C. What is its volume at STP?
10- A metal tank in a garage normally contained compressed air at 4 atm. And 7 °C.
In a fire the tank exploded although it was known to be safe up to a pressure of 14
atm. If you were the detective of the insurance company, what value would you
calculate for the minimum temperature of the fire near the tank?