Thermodynamics (Gases)

Kinetic Theory of Gases

The kinetic theory of gases describes a gas as a large number of small particles (atoms or molecules), all of
which are in constant, random motion. The rapidly moving particles constantly collide with each other and
with the walls of the container. Kinetic theory explains macroscopic properties of gases, such as pressure,
temperature, or volume, by considering their molecular composition and motion. Essentially, the theory
posits that pressure is due not to static repulsion between molecules, as was Isaac Newton's conjecture, but
due to collisions between molecules moving at different velocities.
While the particles making up a gas are too small to be visible, the jittering motion of pollen grains or dust
particles which can be seen under a microscope, known as Brownian motion, results directly from collisions
between the particle and gas molecules. As pointed out by Albert Einstein in 1905, this experimental
evidence for kinetic theory is generally seen as having confirmed the existence of atoms and molecules.

The theory for ideal gases makes the following assumptions:

The gas consists of very small particles. This smallness of their size is such that the total volume of
the individual gas molecules added up is negligible compared to the volume of the container. This is
equivalent to stating that the average distance separating the gas particles is large compared to their
size.
These particles have the same mass.
The number of molecules is so large that statistical treatment can be applied.
These molecules are in constant, random and rapid motion.
The rapidly moving particles constantly collide among themselves and with the walls of the
container. All these collisions are perfectly elastic. This means, the molecules are considered to be
perfectly spherical in shape, and elastic in nature.
Except during collisions, the interactions among molecules are negligible. (That is, they exert no
forces on one another.)
This implies:
1. Relativistic effects are negligible.
2. Quantum-mechanical effects are negligible. This means that the inter-particle distance is much larger than
the thermal de Broglie wavelength and the molecules are treated as classical objects.
3. Because of the above two, their dynamics can be treated classically.
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This means, the equations of motion of the molecules are time-reversible.

The average kinetic energy of the gas particles depends only on the temperature of the system.
The time during collision of molecule with the container's wall is negligible as compared to the time
between successive collisions.
The study of the molecules of a gas is a good example of a physical situation where statistical methods give
precise and dependable results for macroscopic manifestations of microscopic phenomena. For example, the
pressure, volume and temperature calculations from the ideal gas law are very precise.

Boyles Law
Boyle's law shows that, at constant temperature, the product of an ideal gas's pressure and volume is always
constant. It was published in 1662. It can be determined experimentally using a pressure gauge and a
variable volume container. It can also be found through the use of logic; if a container, with a fixed number
of molecules inside, is reduced in volume, more molecules will hit the sides of the container per unit time,
causing a greater pressure.
As a mathematical equation, Boyle's law is: P1V1 P2V2 , where P is the pressure (Pa), V the volume (m3) of a
gas.

Charles's law
Charles's Law, or the law of volumes, was found in 1787 by Jacques Charles. It says that, for an ideal gas at
constant pressure, the volume is directly proportional to its temperature.

V1 V2

, where V is the volume (m3) of a gas and T is the temperature in Kelvin of a gas.
T1 T2

Gay-Lussac's law
Gay-Lussac's law, or the pressure law, was found by Joseph Louis Gay-Lussac in 1809. It states that the
pressure exerted on a container's sides by an ideal gas is proportional to its temperature.

P1 p 2

, where P is the pressure (Pa), and T is the temperature in Kelvin of a gas.

T1 T2

Avogadro's law
Avogadro's law states that the volume occupied by an ideal gas is proportional to the number of moles (or
molecules) present in the container. This gives rise to the molar volume of a gas, which at STP is 22.4 dm3
(or litres).
V V
The relation is given by: 1 2 , where n is equal to the number of moles of gas (the number of molecules
n1 n2
divided by Avogadro's Number which is 6.021023/mol) and V is the volume (m3) of a gas.

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Combined and ideal gas laws

An ideal gas is defined as one in which all collisions between atoms or molecules are perfectly elastic and in
which there are no intermolecular attractive forces. One can visualize it as a collection of perfectly hard
spheres which collide but which otherwise do not interact with each other. In such a gas, all the internal
energy is in the form of kinetic energy and any change in internal energy is accompanied by a change in
temperature.
An ideal gas can be characterized by three state variables: absolute pressure (P), volume (V), and absolute
temperature (T). The relationship between them may be deduced from kinetic theory and is called the

Where
P= Pressure in Pascals (Pa)
V= Volume in m3
T= Temperature in Kelvin
n = number of moles
R = universal gas constant = 8.3145 J/mol K
N = number of molecules
k = Boltzmann constant = 1.38066 x 10-23 J/K = 8.617385 x 10-5 eV/K
k = R/NA
NA = Avogadro's number = 6.0221 x 1023 /mol

number of moles " n"

Mass of gas " m"

Molar mass of that gas " M "

Example 1: Find the volume occupied by 1 mol of an ideal gas at standard temperature of 273 K and
pressure of 1.013105 Pa.
Example 2: A car tyre contains 0.02m3 of air at 27C and a pressure of 3105Pa. What is the mass of the air
in the tyre? (Molar mass of air =28.8 g)

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Thermodynamics
Thermodynamics, which began as an effort to increase the efficiency of steam engines in the early 1800s,
can be thought of as the study of the relationship between heat transferred to or from an object, and the work
done on or by an object. Both heat and work deal with the transfer of energy, but heat involves energy
transfer due to a temperature difference.
The four laws of thermodynamics summarize the most important facts of thermodynamics. They define
fundamental physical quantities, such as temperature, energy, and entropy, to describe thermodynamic
systems and they describe the transfer of energy as heat and work in thermodynamic processes.
Experimentally reproducible distinction between heat and work is at the heart of thermodynamics, and about
processes in which this distinction cannot be made, thermodynamics has nothing to say.

Zeroth law of thermodynamics

The zeroth law of thermodynamics recognizes that if two systems are in thermal equilibrium with a third,
they are also in thermal equilibrium with each other, thus supporting the notions of temperature and heat.
For example, when a scoop of ice cream is placed in a room temperature with a glass bowl, the ice cream
will be melted and the temperature of the bowl will decrease. Likewise, when an ice cube is dropped into a
cup of hot coffee, it melts and the coffees temperature decreases.
Let us consider two objects A and B, which are not in thermal contact, and a third object C, which is our
thermometer. We wish to determine whether A and B are in thermal equilibrium with each other. The
thermometer (object C) is first placed in thermal contact with object A until thermal equilibrium is reached.
From that moment on, the thermometers reading remains constant and we record this reading. The
thermometer is then removed from object A and placed in thermal contact with object B. The reading is
again recorded after thermal equilibrium is reached. If the two readings are the same, then object A and
object B are in thermal equilibrium with each other. We can summarize these results in a statement known
as the zeroth law of thermodynamics (the law of equilibrium).

First Law of Thermodynamics

The first law of thermodynamics is really a restatement of the law of conservation of energy. Specifically, it
states that the change in the internal energy of a closed system is equal to the heat added to the system plus
the work done on the system, and is written as:
Eint Q U
In this equation it is important to note the sign conventions, where a positive value for heat, Q, represents
heat added to the system, and a positive value for work, U, indicates work done on the gas. If energy were
being pulled from the system, as in heat taken from the system or work done by the system, those quantities
would be negative.
In most cases, you will utilize the first law of thermodynamics to analyze the behavior of ideal gases, which
can be streamlined by analyzing the definition of work on a gas.
Since work done U is the force F times distance travel s
U Fs and pressure P = F and therefore F= PA
A
U PAs and Volume is area times change in length V= As
U PV
Due to the sign convention that work done on the gas is positive (corresponding to a decrease in volume),
you can write work as U=-PV.
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Pressure-Volume Diagrams (PV diagrams) are useful tools for visualizing the thermodynamic processes of
gases. These diagrams show pressure on the y-axis, and volume on the x-axis, and are used to describe the
changes undergone by a set amount of gas. Because the amount of gas remains constant, a PV diagram not
only tells you pressure and volume, but can also be used to determine the temperature of a gas when
combined with the ideal gas law. A Sample PV diagram is shown below, showing two states of the gas, state
A and state B.

In transitioning from state A to state B, the volume of the gas increases, while the pressure of the gas
decreases. In the transition from state B to state A, the volume of the gas decreases, while the pressure
increases. Because the work done on the gas is given by U=-PV, you can find the work done on the gas
graphically from the PV diagram by taking the area under the curve. Because of the positive/negative sign
convention, as the volume of gas expands the gas does work (U is negative), and as the gas compresses,
work is done on the gas (U is positive).

Example 3: 5000 joules of heat is added to a closed system, which then does 3000 joules of work. What is
the net change in the internal energy of the system?
Example 4: A liquid is changed to a gas at atmospheric pressure (101,325 Pa). The volume of the liquid was
510-6 m3. The volume of gas is 510-3 m3. How much work was done in the process?
Example 5: Using the PV diagram below, find the amount of work required to transition from state A to B,
and then the amount of work required to transition from state B to state C.

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In exploring ideal gas state changes, there are a number of state changes in which one of the characteristics
of the gas or process remain constant, and are illustrated on the PV diagram below.

The types of processes include:

Adiabatic -- Heat (Q) isnt transferred into or out of the system

Isobaric -- Pressure (P) remains constant
Isochoric -- Volume (V) remains constant
Isothermal -- Temperature (T) remains constant

In an adiabatic process, heat flow (Q) is zero. Applying the first law of thermodynamics, if Eint =Q+U, and
Q is 0, the change in internal energy of the gas must be equal to the work done on the gas (Eint =U).
In an isobaric process, pressure of the gas remains constant. Because pressure is constant, the PV diagram
for an isobaric process shows a horizontal line. Further, applying this to the ideal gas law, you find that V/T
must remain constant for the process.
In an isochoric process, the volume of the gas remains constant. The PV diagram for an isochoric process is
a vertical line. Because U=-PV, and V=0, the work done on the gas is zero. This is also reflected
graphically in the PV diagram. Work can be found by taking the area under the PV graph, but the area under
a vertical line is zero. Applying this to the ideal gas law, you find that P/T must remain constant for an
isochoric process.
In an isothermal process, temperature of the gas remains constant. Lines on a PV diagram describing any
process held at constant temperature are therefore called isotherms. In an isothermal process, the product of
the pressure and the volume of the gas remain constant. Further, because temperature is constant, the
internal energy of the gas must remain constant.
Example 6: An ideal gas undergoes an adiabatic expansion, doing 2000 joules of work. How much does the
gass internal energy change?

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Example 7: Heat is removed from an ideal gas as its pressure drops from 200 kPa to 100 kPa. The gas then
expands from a volume of 0.05 m3 to 0.1 m3 as shown in the PV diagram below. If curve AC represents an
isotherm, find the work done by the gas and the heat added to the gas.

Entropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a
thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only
be driven by convertible energy, and have a theoretical maximum efficiency when converting energy to
work. During this work, entropy accumulates in the system, which then dissipates in the form of waste heat.
In classical thermodynamics, the concept of entropy is defined phenomenological by the second law of
thermodynamics, which states that the entropy of an isolated system always increases or remains constant.
Thus, entropy is also a measure of the tendency of a process, such as a chemical reaction, to be entropically
favored, or to proceed in a particular direction. It determines that thermal energy always flows
spontaneously from regions of higher temperature to regions of lower temperature, in the form of heat.
These processes reduce the state of order of the initial systems, and therefore entropy is an expression of
disorder or randomness. This picture is the basis of the modern microscopic interpretation of entropy in
statistical mechanics, where entropy is defined as the amount of additional information needed to specify the
exact physical state of a system, given its thermodynamic specification. The second law is then a
consequence of this definition and the fundamental postulate of statistical mechanics.
Thermodynamic entropy has the dimension of energy divided by temperature, and a unit of joules per kelvin
(J/K) in the International System of Units.

Second Law of Thermodynamics

The Second Law essentially says that it is impossible to obtain a process where the unique effect is the
subtraction of a positive heat from a reservoir and the production of a positive work. Energy exhibits
entropy. It moves away from its source. In this sense, energy or heat cannot flow form a colder body to a
hotter body. You cannot keep a continual flow of heat to work to heat to work without adding energy to the
system. In machine terms, you have to add energy to get more work, and the ratio of heat to work will never
equal 100% due to energy expanding away from its source.
The second law of thermodynamics also limits the efficiency of any heat engine, and proves that it is not
possible to make a 100 percent efficient heat engine, even if friction were completely eliminated.
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Third Law of Thermodynamics

The Third Law explains this further. It says that all processes cease as temperature approaches absolute zero.
This is the temperature at which molecules cease movement, cease producing kinetic energy. In other words,
there is no energy. In other words, the third law of thermodynamics states that if all the thermal motion of
molecules (kinetic energy) could be removed, a state called absolute zero would occur. Absolute zero results
in a temperature of 0 Kelvins or -273.15 Celsius.
Absolute Zero = 0 Kelvins = -273.15 Celsius
The Universe will attain absolute zero when all energy and matter is randomly distributed across space. The
current temperature of empty space in the Universe is about 2.7 Kelvins.

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