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Farah
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Abstract
A detailed overview of the origins and possible derivations of the ideal
gas law are given in this lecture text. The tacit assumptions in the usual
textbook derivations are identified and ways of thought are proposed to
justify their use. It is shown that the solution of the Schrödinger equation for
the particle in a box model is very closely connected to the ideal gas law. A
detailed derivation is presented on how equipartition and the Boltzmann
distribution lead to the velocity and speed distributions observable in ideal
gases. Major emphasis is given to the mathematical consequences of the lack
of direction dependence in these properties. General formulas are introduced
and proved to describe the thermodynamics of ideal gases. During the
derivations, a method for students to employ computer-aided symbolic
calculations using the Wolfram Alpha web-based service is also described.

Keywords Equipartition · Boltzmann distribution · Maxwell-Boltzmann

speed distribution · Particle in a box · Thermodynamics

Introduction

Gases play a fundamental role in teaching chemistry. Their formation is

usually easily observed in chemical reactions, and the quantitative laws of
their behavior give the most direct connection between macroscopic and
particle-level properties. Even in the history of science, discovering that gases
have mass was very important in formulating the law of mass conservation,
which was one of the starting points for establishing chemistry as an
independent field of science in the late eighteenth century [1–4]. Gas laws are
typically taught in high schools or in introductory chemistry courses at the
university level education [5–8].
The ideal gas law was probably first stated by Benoît Paul Émile Clapeyron,
who combined a number of known empirical laws such as Boyle's law,
Charles's law, Avogadro's law, and Gay-Lussac's law [9]. Today, the most
commonly written form of the ideal gas law is:
pV = nRT = NkT.

In this formula, p is the pressure, V is the volume, n is the amount of

substance, R is the gas constant (8.314 J mol−1 K−1), T is the temperature
(K), N is the number of particles present (dimensionless), and k is the
Boltzmann constant (1.381 × 10−23 J K−1).
The commonly used form in Eq. 1 has a drawback from a physical
chemistry point of view. Two of the physical properties in it, the amount
of substance (n) and the volume (V), are extensive quantities (i.e., they
depend on the size of the sample). When characterizing the chemical
properties of something, there is seldom much interest in the amount of
the sample: a drop of pure water and a large swimming pool of pure water
contain the very same material. This means that physical chemistry is
mostly interested in intensive quantities, those which are independent of
the size of the sample. One possibility to give the ideal gas law using
intensive quantities only is to introduce the property molar volume (Vm)
as the ratio of volume and amount of substance:
pVm = RT.

Note that instead of four physical properties and a universal constant as

in Eq. 1, we now have three properties and R in the equation. It is an
equation of state, and the number of properties in it is not accidental:
Gibbs’ phase rule (p. 123 in [8]) requires that a one-component system
with one phase (gas) has two degrees of freedom. If we specify two
properties, all others are set and must be obtainable through some sort
of equation. The phase law does not say which physical properties should
be specified; this is a matter of choice.
As an alternative to Eq. 2, the reciprocal of the molar volume, molar
concentration (c) may also be used in an intensive-only form of the ideal
gas law:
p = cRT.

This form is particularly useful when an analogy is drawn with it to

introduce the van’t Hoff equation for calculating osmotic pressures (p.
163 in [8]). The detailed text of this article will rely on some commonly
known physical concepts (mass, velocity, momentum, energy, etc.). The
most recent edition of the textbook of Atkins, de Paula, and Keeler [8]
will be used in the text whenever a background reference is needed. Two
important laws are worth stating even at this introductory point. The first
is the equipartition theorem (p. xxxviii in [8]), which states that in a
system in thermal equilibrium, on average, an equal amount of energy
(½kT) is associated with each degree of freedom. The second one is the
law behind the Boltzmann distribution (p. xxxvii in [8]): in a system of
thermal equilibrium, the ratio of the population of two states
characterized by a difference of energy E is e−E/(kT).

The concept of ideal gas and derivation of the ideal gas law

The notion of an ideal gas

The concept of an ideal gas follows naturally from a particle-based view of

matter. Some textbook authors prefer the term ‘perfect gas’ arguing that the
word ‘ideal’ is usually used with a different meaning in physical chemistry
[8, 14, 15], but others seem to have understandable reservations against
calling any material ‘perfect’ [5–7]. In any case, this is a matter of language
preference rather than a true scientific issue. This text uses the term ‘ideal gas,’
which reflects the personal choice of the authors.
In an ideal gas, particles move randomly and independently of each other; the
only interaction between them is that they occasionally collide [8, 16–18]. These
collisions are elastic, which means that the laws of momentum conservation and
energy conservation can be stated for them in a simple manner.
Momentum is the product of the mass (m) and velocity (v) of an object. Mass is
a scalar quantity in physics, but velocity is a vector that can often be conveniently
stated with three independent components in a Cartesian coordinate system (vx,
vy, vz, all three can be both positive and negative). Therefore, momentum is also
a vector, and the conservation law directly applies to each of its components.

Some confusion may arise from the fact that the quantities' velocity and speed
are not always distinguished clearly. In this text, we will strictly stick to the
convention that speed
(s) is the size of the velocity vector. Therefore, it is a scalar quantity without
direction, and it cannot be negative. Speed can be calculated from the velocity
vector using a simple geometric argument (Pythagorean theorem):
S=√ v2 + v2 + v2.
x y z

Note that it is impossible to obtain the velocity from the speed alone, and
confusion often arises from the fact that the symbol v is used for speed as well.
The law of momentum conservation is straightforward in physics and can be
applied to non-elastic collisions as well. The law of energy conservation is
somewhat different. There are many different kinds of energy (e.g., electric,
rotational, vibrational), but for an ideal gas, the only thing we care about is
kinetic energy. This can be calculated by multiplying the mass with the square
of the speed and then dividing by two, or also with the components of velocity:

Therefore, kinetic energy is a scalar quantity (this is of course, valid for all kinds
of energy). The assumption behind an elastic collision is that the particles do not
change any of the other kinds of energy in it: they do not get irreversibly
deformed, and if they rotate or vibrate, they do so in the same way after the
collision. This means that the sum of the kinetic energies of the two colliding
particles is the same before and after the encounter.
Two particles that are involved in a collision have six velocity components
combined. Even if we know all of them before the collision, they will take new
values after the event, so six unknowns arise. There will be three equations from
the conservation of momentum (one for each component) and one additional
equation from the conservation of energy. This means four equations altogether,
which is not enough to define six unknowns. It is prob- ably good to remember
that considerations beyond the conservation laws are needed to calculate the
outcome of an elastic collision, but fortunately, these are not necessary in
dealing with the properties of ideal gases.
Many statements can be made about an ideal gas [5–8, 16–18], but the following
is already sufficient as a physical definition: the only possible interaction
between the particles is the elastic collision. Note that the concept is a scientific
abstraction, and a substance in itself cannot be called an ideal gas. For example,
hydrogen and helium are not ideal gases in a strict sense. The precise statement
is always that a certain substance behaves like an ideal gas under certain
conditions. For hydrogen and helium, certain conditions include room
temperature and atmospheric pressure. Even gold behaves like an ideal gas at
3500 K and 1 Pa.

Notably, the definition given above does not require identical particles in the
gas. It can be a mixture of different substances. Most of the intensive physical
properties of an ideal gas depend on the chemical composition. An obvious such
property is molar mass (M); additional examples include density (ρ) and molar
heat capacities (CV,m and Cp,m). There are few exemptions: for example, pressure,
temperature, molar volume and concentration. These are the ones used in Eqs.
2 and 3, and this is a pivotal point in ideal gas behavior: one does not need to
know the identity of the gas to work with these selected properties. This is the
very reason why the forms given in Eqs. 2 and 3 are highly preferred to all other
possibilities. Also, this was the essential discovery in Avogadro’s law [19, 20]. It
should be noted that the elastic nature of the collisions between particles is
emphasized in most textbooks (p. 11 in [8]). However, from a strict physical
point of view, this is only true if the particles are structureless (e.g., noble gas
atoms). In multiatomic molecules, there are additional internal forms of
molecular motion that can store energy, most importantly rotations and
vibrations.
In a collision, it may happen that these are increased at the expense of the overall
kinetic energy, or their decrease provides extra kinetic energy. Fluctuations of
this kind are possible, but the equipartition theorem guarantees that the two
conservation laws behind elasticity will be valid statistically over a large number
of collisions. Also, an individual collision with the wall seems to violate the
conservation of momentum as the particle bounces back (the direction of the
velocity changes) without any counterpart, as the wall is stationary. This picture
is still useful as the wall is considered to have such a large mass that gaining a
little bit of momentum from a molecular collision will not change its state of
motion. In addition, similarly to the intermolecular case, the overall efect of a
large number of molecular collisions with all parts of the container wall will give
an average of zero change in the overall momentum.
A simplistic view of pressure

A sequence of thought presented in many textbooks will be reproduced here (p.

11 in [8]). Imagine a sample of ideal gas composed of only one substance, and
attempt to calculate the pressure using the scheme shown in Fig. 1. Notice that
this shows three different two-dimensional projections of a three-dimensional
system, which are not always easy to understand intuitively. In this scheme, A is
a flat surface whose plane will sometimes be referred to as the wall; M1, M2, M3,
M4, M5 and M6 are particles; the arrows drawn represent velocity vectors of the
parti- cles. The middle view is a perspective one, the left view is taken in a
direction parallel to surface A, whereas the right view is from a direction
perpendicular to A. As all particles are identical, the arrows are also proportional
to the momenta of the particles. Consider A (notice the italics, meaning that it is
a physical property now rather than a geometrical element), the area of the flat
surface A. For simplicity, a square is drawn as A in Fig. 1, but the following
arguments are valid for all shapes, even ones with curved boundaries. Try to
count the particles colliding to this surface in a time interval of Δt. (Symbol Δ is
a capital Greek delta, the fourth letter in the Greek alphabet. This notation is
very common, but not particularly didactic as in a single scientific symbol.

Fig. 1 Particles and

velocities considered for
the derivation of
pressure in an ideal gas
(three different views).
A: Flat surface upon
which the pressure is
calculated; M1, M2, M3,
M4, M5, M6: individual
particles; arrows:
velocities of particles; v:
velocity of particle P; vx:
velocity of particle M1 in
direction x

This could be difficult to distinguish from the product of two symbols. Similar
notation customs are used for differentials with the letter d and for partial
differentials with the symbol ∂.) Some knowledge of the velocities of the
particles is necessary to do this, but only in the direction that is perpendicular
to the chosen surface A. Let the symbol for this direction be x. Consider particle
M1, whose velocity component in the direction x is vx. If vx is the same as the
average of this property for all particles, then half of the articles in the
rectangular box of base A and depth vxΔt collide with A in this interval. The
reason why only half of the particles do this is that in truly random motion, the
other half moves away from A and will not collide within time Δt. The volume of
the box is AvxΔt, so using the concentration (c) of the gas, the amount of
substance for the colliding particles is cAvxΔt/2. The number of such particles is
obtained by multiplication with the Avogadro constant NA (= R/k) to yield
NAcAvxΔt/2.
Our main interest is the pressure, which is defined in physics as force divided by
the area upon which it acts. Furthermore, force is described in Newton’s laws as
the overall momentum change divided by the time interval in which it occurs.
When particle M1 collides with the wall, it is a very special kind of collision: a
bounce (meaning that the mass of the wall is so much higher than the mass of
the molecule that the wall does not move at all). The physical laws of bouncing
require that the velocity of the particle in direction x changes from vx to − vx,
while other components remain unchanged. This is shown by a dotted black
arrow in Fig. 1. So, the overall change of velocity in direction x is |− vx− vx |= 2vx
(the | | signs represent absolute value). If the mass of the particle is m, this
means a momentum change of 2mvx. Therefore, the pressure is obtained by
multiplying this momentum change (2mvx) with the number of particles
colliding (NAcAvxΔt/2) and then dividing by the time interval (Δt) and the
surface area (A):

It can be seen that the surface area and the time interval conveniently disappear
during simplifcation, which is readily rationalized by the physical observation
that the pressure of a sample of gas is independent of where and when it is
measured. As already mentioned, the simple sequence of thought leading to
Eq. 6 can be found in many textbooks as a derivation of the ideal gas law,
although the work used as a reference here [8] was notably improved compared
to its original version with the publication of new editions. However, this
derivation is seldom taken to completion. Instead, Eq. 6 is typically simply
compared to the ideal gas law (whose validity is assumed before the end of the
derivation!), and a formula is obtained for vx. This typical approach is most
unfortunate as there is a simple line of thought that can be used to complete the
derivation easily. This relies on the equipartition principle: first, the term mvx 2
/2 is recognized as the contribution of the motion in direction x (Ex) to the
average kinetic energy of the particles; then, the equipartition principle is
applied to replace this term with kT/2:
It is seen that we arrived at the form of the ideal gas law written in Eq. 3, so the
derivation is complete now. Historically, this equation could be used to define
the universal constants k and R. As already pointed out, textbooks typically do
not bring the derivation to completion. In the absence of the use of equipartition,
this is not even a proper derivation of the ideal gas law. However, there are other
problems with the presented sequence of thought as well. The reader is asked to
stop for a moment at this point and try to find lapses of logic in the sequence of
thought presented above in Sect. "A simplistic view of pressure." Normally, few
people are inclined to do this as textbook knowledge is assumed to be beyond
any doubt. Unfortunately, this is far from the truth. Similar to all other
documents, textbooks also contain errors, which may range from minor typos
or regrettable omissions to outright fallacies. The next subsection will list a (not
necessarily complete) collection of such lapses of logic in this sequence of
thought. None of them are entirely beyond repair, but they necessitate
additional remarks at the very least. If the reader was successful in identifying
one or more of them, it is a favorable sign of the ability to think scientifically.

Direction

Consider particle M4 in Fig. 1. It is within the rectangular box we are interested

in, but is moving away from surface A, so its velocity component in direction x
is negative and will not hit A. This is why we divided the number of particles in
the rectangular box by 2, right? However, we took vx as the average for all
particles. Since the velocity components can be both positive and negative, and
the motions are totally random, the average will certainly be 0. One might be
inclined to update the definition by declaring that vx should be the average for
those particles that move toward A, but this still leads to problems that are
described in Sect. "Averages."

Entering and leaving

Consider particle M3 in Fig. 1. It is not within the rectangular box for which we
have made the count, but it does collide with A within the given time interval.
Or consider particle M2. It is within the box; it moves toward A but collides with
the wall outside A. So, M3 is not counted but contributes to the pressure,
whereas M2 is counted but does not, in fact, contribute. Refuge from this
problem can be found in the fact that there is a very large number of molecules
in the system, and their motion is completely random, which gives a good reason
to hope that the effects of entering and leaving particles will cancel each other
out exactly.

Collisions

Consider particles M5 and M6 in Fig. 1. They are both within the rectangular
box of interest, and they are both moving toward A. However, they collide with
each other before hitting the wall (only the left view of Fig. 1 shows this fact
clearly) and change the direction of their motion. There are several good
remedies for this problem. The first is noticing that the conservation of
momentum law is valid separately for the different components of the vector. As
the collision cannot change the sum of the momenta of the two particles in
direction x, this momentum will reach surface A and exert a force despite the
intermolecular collision. The second is based on the fact that all appearances of
the time interval Δt are cancelled by the operations in Eq. 6. That means we are
free to select a Δt that is short enough to avoid any such collisions. The third way
out is a highly counterintuitive one: we did not clearly specify this earlier, but
we imagine the particles to be mass points at the first approach [21]. Roughly
speaking, points do not have measurable sizes in any direction, so they do not
collide. To satisfy even the most pugnacious mathematician, the probability of
two mass points colliding in this model is zero in any finite time interval. A
simultaneously amusing and amazing further fact in probability theory is that
an event with zero probability is still not impossible [22]. This line will not be
pursued here any further: understanding the quantitative description and the
consequences of collisions between particles in an ideal gas needs such scientific
depth that a separate article will be devoted to it.

Relativity

The subtitle is honest here but may still be misleading. No, we will not argue that
Einstein’s relativity theory should be brought into the discussion in any way.
What we simply mean is that reference points are needed to measure velocity or
speed. These very often take the form of a coordinate system. The derivation
presented to calculate the pressure tacitly assumed that the wall itself does not
move; only the particles change their positions. So, the coordinate system is
fixed to the container of the gas sample. Still, we were notably free to choose a
direction to be designated x. There will be some consequences of this freedom,
which we will discover in a later section. Also, at this point, it may be useful to
state that most of the derivations presented in this article are only valid if the
center of mass of the gas sample does not move relative to the container. In other
words, transferring the results to the case of following gases would need
additional mental work.

Averages

Now, compare the velocities of particles M1, M2, M3, M4, M5, and M6 in Fig. 1.
Of course, they are different because the directions of movement are different.
However, a closer look will reveal that even the speeds are different. This is a
natural state of affairs in a gas sample: the hypothetical state in which all the
particles move with the same speed is definitely outside the boundaries of
classical thermodynamics.

The speeds and velocities of different particles vary then; yet, we used a single
value for vx. First, we tried to define it as a bona fide average and then attempted
to update the definition to require an average for those particles that move
toward A but warned that this would create even more problems. Now, it is time
to deliver on this promise. The problem is averaging itself, which can be
demonstrated in an example that requires some numerical calculations.
Consider two gas particles moving at different speeds, for example, two helium
atoms, one moving at 100 m s −1, the other one at 500 m s −1. It is a very natural
thing to state that the average speed of the two molecules is 300 m s−1 in this
case. Now, calculate the kinetic energy of the two particles (E=ms2 /2). The
mass of a helium atom is m = M /NA =0.00400 kg mol−1/6.02× 1023
mol−1=6.64× 10−27 k g, so the kinetic energy of the one traveling at 100 m s−1
is 3.32× 10−23 J=33.2 yJ (y stands for yocto, a rarely used prefx for 10−24) or
20.0 J mol −1. The kinetic energy of the helium atom moving at 500 m s −1 is
830 yJ (or 500 J mol−1), so the average energy of the two atoms is 432 yJ or
260 J mol−1 (note that the decimal part is not given, as this would run against
the established scientifc use of signifcant digits). If one calculates the kinetic
energy for the average speed of 300 m s −1, the result is 299 yJ (180 J mol−1).
There is no mistake here: the average energy cannot be calculated from the
average speed! Or at least not from this average. When discussing the
description of ideal gases, many textbooks introduce the concept of root mean
square speed, which is, as the name implies, the square root of the average of
the squares of the two speeds, srms=((1002+ 5002 )/2)1/2= 361 m s −1. If the
average energy is calculated from srms, the correct value of 432 yJ (or
260 J mol−1) is achieved.

The origin of the problem is quite deep. When we consider a large collection of
things (such as molecules) whose properties differ, there is no natural way of
calculating ‘the average.’ There are several different averages [22]. The one that
seems the most natural to many users is called the arithmetic mean: we add all
the properties and then divide by the number of things considered. The root
mean square has the mathematical name of quadratic mean, and there are
others as well. When we try to characterize the properties of a bunch of particles
with different individual properties, it is difficult to know which of the means is
needed in a formula. It is often necessary to explore the probabilities at which
certain values occur in a physical property. This idea will be elaborated in later
sections.

Quantum mechanical origins

A careful reader might have already spotted an apparent contradiction. The end
of Sect. "The notion of an ideal gas" defined the ideal gas as a sample for which
the only possible interaction between the particles is the elastic collision. On the
other hand, Sect. "Collisions" said that if the particles of an ideal gas are thought
to be mass points, they collide with zero probability. This may simply be a
language issue, but by formal logic, the absence of collisions actually still
satisfies the ‘only possible interaction…’ criterion. The easiest way to exclude the
possibility of collisions is to have only one particle in a container.

Could one particle make sense as an ideal gas? It certainly collides with the walls
of the container, so it must exert some pressure. It is more difficult to imagine
how we could attribute temperature to a single particle. Nevertheless, it is worth
putting some effort into this as it is an exceptionally well-characterized system
in quantum mechanics for which a reasonably detailed mathematical
description is given in textbooks as well. It is called particle in a box (p. 264 in
[8]).
All the physical properties of a particle in a box in thermodynamic equilibrium
can be obtained from its stationary wave function Ψstat, which is the solution of
the stationary Schrödinger equation:

In this equation, x, y and z are the spatial coordinates in a Cartesian system, m

is the mass of the particle, E is the energy of the particle, h is the Planck constant,
π is the well-known constant equal to the ratio of the circumference and
diameter of a circle (3.1415…), and V(x,y,z) is the potential function that
characterizes the interaction of the particle with the outside world. The form of
V(x,y,z) for the particle in the box model is such that it is 0 within the box,
whereas it is infinitely large outside the box. This partial differential equation
resembles a single algebraic equation for more than one unknown, in which
there is no single solution; the best we can achieve is to find a connection
between the unknowns. Similarly, in a partial differential equation, the
“solution” is a connection between the independent variables. However,
typically, there are other, non-differential equations that must also be satisfied
by the wave function in addition to the Schrödinger equation.

In the particle in a box model, these additional equations are called boundary
conditions, and they reflect the physical fact that the particle cannot occur in or
outside the walls of the container. For a rectangular box of dimensions a×b×c,
these boundary conditions can be stated in a simple manner:

Finding the solution of a partial differential equation is usually not an easy

process. One can certainly look for help from software such as Wolfram Alpha
[13], but in the case of Eqs. 8–9, this is not necessary as the solution is given in
many textbooks. It takes the following form (p. 269 in [8]):
The energy of a particle in a box is quantized. The expression giving the possible
energy levels contains three quantum numbers (nx, ny, nz) that are independent
of each other and characterize the movement in the three spatial directions (p.
270 in [8]):

As already stated, finding the solution shown in Eqs. 10–11 is quite a demanding
task, but once known, it is easy to make sure that it satisfies the equations by
simple substitutions.

As a next step, we can calculate the force acting on one of the walls of the box.
Since force does not appear in any of Eqs. 8–11, it must be connected to the
existing physical properties somehow. For this, it is useful to recall a piece of
basic physical knowledge: energy is the ability to do work, and work can be
calculated as the product of the force and the displacement in the direction of
the force. So, when the wall of the rectangular box in direction x is moved a bit,
the force can be calculated as the ratio of the energy change and the
displacement in direction x. In more formal mathematical language, it is said
that the force is the derivative of the energy regarding a change in the side length
a. As the energy is already known as a function of a, this calculation can be
brought to an easy conclusion:

In an ideal gas, the particles are independent of each other, and if they are
considered mass points, they do not collide with each other. So, for N particles
(N=nNA), the overall force is obtained by simply summing the contributions
from the individual particles:

At this point, we can use the equipartition theorem again. The fact that the
average energy per degree of freedom for a single molecule is kT/2 can be put
into a mathematical equation for our case as follows:

The pressure is the absolute value of force divided by the area of the
wall perpendicular to direction x, which is easily given by the product
of the two sides (bc):

So, the most common form of the ideal gas law (Eq. 1) can be derived
directly from the quantum mechanical model of a particle in a box.

Thus far, this derivation was presented for a rectangular box. However,
the ideal gas law, in fact, has no limitations on the shape of the box in
which the gas is stored. The previous considerations can be somewhat
extended into containers of different shapes, but these rely on solving
the stationary Schrödinger equation for different boundary conditions.
While a particle in a (rectangular!) box is a typical textbook model in
quantum mechanics, other cases are seldom handled. This article gives
two more examples: the case of a cylindrical box and the case of a
spherical box.
A cylindrical box is imagined in a way that the cross section of the box
in the yz plane is a circle of radius R, whereas in the two other
perpendicular planes, it is a rectangle. The height of the cylinder is
denoted a; its meaning is exactly the same as that of c for a rectangular
box. The details and the solution of the Schrödinger equation are given
in the Supplementary Information. What is important is the formula
obtained for the possible quantized energy levels of a particle. This
contains an nx quantum number analogous to that seen in Eq. 9. There
are two additional quantum numbers that arise for motion in the
direction perpendicular to the x-axis, but they do not appear in the
energy formula. Instead, a series of infinitely many isolated values
denoted Zml appear, which represent the independent variables at
which the value of the Bessel function of the first kind is 0. This might
sound like a frightening definition, but for our purposes, it is a constant
whose values will not even be needed. The full energy formula is:

Now, two different ways of calculating pressure arise. First, the

collisions of the “side” of the cylinder must be considered. The force
here is the derivative of the energy with respect to R, the radius of the
cylinder:

In calculating the pressure, it must be considered that the movement

characterized by radius R is two-dimensional now, which means that
the average energy will be 2×½kT. The surface to be considered is the
curved surface of the cylinder here (2πRa):

The same can be done in the direction z, which would give the pressure
acting on the bases of the cylinder. The force here is calculated by
derivation with respect to a:

Since z is a single dimension here, ½kT is necessary for energy. The

surface is the area of the circular base of the cylinder:

The case of the spherical box (with radius R) also brings some
difficulties in solving the stationary Schrödinger equation; the solution
is shown in the Supplementary Information. The quantized energy
levels are given by a formula that includes a constant Zl, which
represents the independent variables at which the value of the
spherical Bessel function of the first kind (jl ) is 0. Again, the actual
values of Zl will not be needed:

The force acting upon the spherical wall is obtained from a derivation
similar to the previous ones:
Now, R characterizes the boundaries of a three-dimensional
movement, so the average energy should be taken as 3×½kT. For
calculating the pressure, the surface of the sphere is needed now:

In all cases (Eqs. 15, 18, 20, and 23), the validity of the ideal gas law is
confirmed for containers of different shapes. However, it must be
recognized that only simple shapes can be handled by this method, and
even then, the derivation is notably burdensome as it involves finding
the solutions of the stationary Schrödinger equation with different
boundary conditions. So, overall, this line of thought shows quite
nicely the fundamental origins of the ideal gas law but is very
impractical as a proof and becomes close to impossible for more
complicated container shapes. So, in the next section, a line of thought
will be sought where the container shape does not matter so much.

Speed and velocity distributions in ideal gases

As already pointed out, different molecules in a gas sample move with

different velocities and speeds. One way to cope with this problem is
to use averages, but the calculation of an average causes a loss of
information content because we record only one number instead of a
series of numbers. A more sophisticated approach is based on
distributions: we seek to give the probability of the occurrence of
certain values in the sample. Thus far, we have dealt with energies; it
is now time to transform them into speeds and velocities. Fortunately,
the movement components of a particle in the three spatial dimensions
are statistically independent of each other. Therefore, if we find a
suitable description in one dimension, the rest can be done by
mathematical considerations only, without needing further physical
insight.
One dimension: normal distribution
The kinetic-molecular theory of gases assumes that molecules only
have kinetic energies associated with their translational motion. As
already pointed out, the potential energy within the box is 0, which
means that the particle only has kinetic energy. These two facts nicely
coincide, so the kinetic energy of a particle can be equated to the
discrete energy levels obtained as a solution of the Schrödinger
equation.

To calculate the probability of the occurrence of a certain energy, we

must rely on the Boltzmann distribution. As already explained, this
says that the ratio of probabilities of two states can be calculated using
an exponential function, the exponent of which features the energy
divided by a kT term. Overall, the probability of the movement with
translational quantum number nx, denoted P(nx), is given by the
following equation:

The logic of constructing this formula is that the Boltzmann

distribution makes a direct statement about the ratio of two
probabilities rather than the specific probability of a selected state. In
the enumerator, there is one specific ratio, whereas in the
denominator, the ratios for all possible states are summed. This
ensures that the formula yields conventional probabilities: they are
between 0 and 1, and adding all of them gives 1 as a sum:

To pave the way forward, we will calculate a cumulative probability,

which is a sum of individual probabilities. It is especially important to
calculate the (cumulative) probability that the value of nx is not larger
than a pre-fixed value. Occasionally, it may be a source of confusion,
but it is customary to avoid introducing a new symbol for this pre-fixed
value and denote it nx. The formula for the cumulative probability is
then given as:

There are two unfortunate features of Eq. 26. First, the use of the letter
F to denote a cumulative probability function is almost exclusive in the
literature. In this article, F was already used for the physical property
of force, which is also an almost exclusive notation in science. The only
remedy that can be offered is that F used for a cumulative probability
function is always followed by parentheses, and this is never done for
force. The second mishap connected to Eq. 26 is mathematical: the
infinite sums appearing in it are quite difficult to calculate. It is
absolutely necessary to take an approximation step, which is based on
the observation that at temperatures > 10 K, the P(nx) probabilities
corresponding to two neighboring nx values are barely different. The
consequence is that the possible nx values can be approximated well
with a continuum instead of quantized, discrete values. The continuum
equivalent of addition is integration, so we can replace the infinite
sums in Eq. 26 by infinite integrals, which is more helpful than it
seems at first sight because there is a huge, time-honored experience
in calculating infinite integrals in mathematics. This transition uses
the fact that the histograms that would be drawn with an interval of 1
(Δi = 1) to calculate the infinite sums can be approximated well by the
area under the continuous curve drawn to the top of the intervals:

In this case, a very good approximation can be given for the cumulative
probability function:

In Eq. 28, the notation erf refers to a function of high reputation in

mathematics, called the error function [22]. Its definition is based on
the integral of an exponential function where the independent variable
in the exponent is squared:
In Eq. 29, the symbol ξ is a small Greek xi letter. It is often used in
mathematics when a letter is needed for an independent variable with
no physical meaning. Introducing variable w serves a similar purpose.
Note that thus far, we have used a one-dimensional box as we are
interested in the distribution of the velocity component in one
direction. Now, this velocity component is calculated from the fact that
all of the energy of the particle is kinetic energy:

Although this might seem an obvious way of calculating the velocity

component from the corresponding energy, we are making a lapse of
logic at this point. Equation 30 is time-honored classical physics, but
in fact, it is not the way quantum mechanics works, where every
physical property has an operator and is calculated from the wave
function. Also, the wave function from which the sequence of thought
originates is a stationary wave function, for which the classical notion
of a single particle traveling with a velocity v does not make sense. An
elegant way to avoid this problem is using the partition function in
statistical thermodynamics, but it is beyond the scope of the present
text. Fortunately, even with this laxer attitude, the final result will be
useful and not incorrect.

Substituting the formula given in Eq. 30 into the distribution shown in

Eq. 28 will yield the form of the cumulative distribution function as a
function of vx. However, we now need to incorporate the fact that we
think of vx in classical physics as a signed quantity that can be either
negative or positive. By symmetry, we know that the probability of −vx
and +vx must be the same, so the cumulative distribution function
must be 0.5 for the vx value of 0. This sequence of thought leads to the
following distribution:

The derivative of a cumulative distribution function is called the

probability density function, which is usually denoted f. As erf was
defined based on an integral in Eq. 29, it is not very difficult to find its
derivative:
Now, we have completed the most important task in this article: we
have formulas that describe the distribution of component x of the
velocity of a particle in an ideal gas. The cumulative distribution and
the probability density functions are shown in Figs. 2 and 3. Note that
these are scaled graphs: rather than imagining a particular particle
(with a defnite value of m), and at a given temperature (T), the axes are
scaled with these quantities so that the graphs can be used for every
ideal gas at all temperatures. Both graphs show vx as the horizontal
coordinate; the scaling constant is (2kT) ½ m−½ for this property. For
helium gas at 600 K, 1 on this axis would correspond to 1578 m s−1,
whereas for sulfur dioxide at 300 K, the unit would be 279 m s −1.

kjhkjhj
Fig. 2 Scaled cumulative distribution Fig. 3 Scaled probability density
function for component x of the velocity function for component x of the
of a particle in an ideal gas velocity of a particle in an ideal gas

The vertical coordinate is a probability in Fig. 2, so it is dimensionless.

For the probability density in Fig. 3, the vertical coordinate has the
inverse dimension of vx, so the scaling constant is (2kT) −½ m½. As
fully expected, based on the definition, F(vx) is a monotonic function:
it starts from 0 and reaches 1 at the positive infinity limit. Its derivative
has a maximum at vx=0, and the area under the full curve is 1
(dimensionless).

It is likely that the curve shown in Fig. 3 looks very familiar to most
readers with some scientific background. The curve itself is called a
Gaussian curve; the distribution it represents is called a normal (or
Gaussian) distribution. The general form of its probability density
function is this:
The two parameters in the general form are called expectation (μ) and
standard deviation (σ). A comparison of Eqs. 32 and 33 show that
these parameters have the following value for the distribution of
component x of the velocity of a particle in an ideal gas:

So, the mathematical content of Eq. 32 is that vx is a normally

distributed random variable with expectation 0 and standard deviation
k½ T½ m−½.

The appearance of the normal distribution is actually very good news,

as this is one of the most common and well-known distributions in
probability theory [22]. The zero expectation discovered in Eq. 34 has
some significant physical content: it is the mathematical form of the
fact that the coordinate system is fixed to the rigid container, where
the center of mass of the gas sample is stationary. The distribution is
symmetric, which is an even stronger statement mathematically; the
same absolute value of component x of the velocity is equally probable
no matter what direction (positive or negative) is considered.

The one-dimensional distribution shown in Eq. 32 is frequently given

in textbooks (p. 13 in [8]). However, there is a grossly neglected point
here. There is no a priori dedicated x direction in a sample of gas; the
observer is free to choose any direction and label it as x. This means
the one-dimensional distribution must be the same in every direction
we can select. It is not enough to only state that the same distribution
will be seen in the two perpendicular directions (y and z), which are
independent of x; rather, it will be in all the directions. It must be
shown that the distribution in Eq. 32 has this fundamentally important
property.

We can select any direction in a three-dimensional space by giving two

angles, very similarly to the way it is usually done for spherical
coordinates as shown in Fig. 4.

These spherical angles are usually denoted φ and θ. For spherical

coordinates, it is known that its x coordinate for a vector with angles φ
and θ is its length multiplied by a factor of cosφ sinθ. However, here,
the two directions (x and the one identified by φ, θ) are
interchangeable. So, a segment of length vx in direction x has a
perpendicular projection in direction φ and θ with a length of vx cosφ
sinθ. Similarly, vy in direction y would have a projection of length vy
sinφ sinθ, and vz in direction z would have a projection of length vz
cosθ.

velocity components vx, vy, and vz are independent random variables.

If they are given, then the velocity component vθ,φ is simply the sum
of the three projection lengths:

Fig. 4 Connection between the

components of a vector and its
polar angles φ and θ

What we do here is quite common in probability theory: a new random

variable is formed by combining existing, independent random
variables. As the direction φ, θ was selected to begin with; the
trigonometric functions are simple constants in this formula rather
than variables.

As already remarked, there is a lot of knowledge about normal

distributions in probability theory. For example, it is known that if a
normally distributed random variable ξ with expectation μ and
standard deviation σ is multiplied by a constant α, then the resulting
new random variable αξ will be normally distributed with expectation
αμ and standard deviation ασ. Furthermore, if two independent,
normally distributed random variables ξ 1 and ξ 2 with respective
expectations μ1, μ2 and standard deviations σ1,σ2 are added, the result
will still be a normally distributed random variable ξ 1+ξ 2 with
μ=μ1+μ2 and σ=(σ1 2+σ2 2 ) ½ [22]. Some clues on the proof of these
obvious-looking, yet far-from-self-explanatory properties are given in
the Supplementary Information.

Using these rules in Eq. 35 reveals that the resulting vθ,φ random
variable, constructed by the linear combination of vx, vy and vz, is
normally distributed with an expectation of zero. Its standard
deviation σθ,φ can also be calculated from the standard deviations of vx,
vy and vz (σ = k½ T½ m−½):

So, these considerations show that in any direction, the speed

distribution is a normal distribution with the same mean and variance
as in the x, y, or z directions, which confirms the independence of the
speed distribution from the direction.

Direction independence might seem a casual property. However, it is

a very important one even beyond the obvious physical requirements.
For example, direction independence alone prohibits having an upper
limit on the speed of one particle, even without any knowledge of the
form of the distribution. Suppose that there is such an upper limit
(vmax) so the distribution in any direction would give zero probability
for any velocity component exceeding vmax. This would, therefore, be
true for x, y, and z directions as well. However, if one selects the
direction φ=45° and θ=45°, for example, Eq. 35 shows that the
maximum in this direction is vmax(1+ 2½)/2, which is larger than
vmax. This contradicts the assumption that the speed cannot be larger
than vmax in any direction. Therefore, the speed of a particle cannot
have an upper limit in the mathematical sense. Not even extremely
high-velocity components are impossible; they are only improbable.

Collisions with the wall, pressure, and means

The distribution obtained in Eqs. 31–32 makes it possible to develop
the simplistic view of pressure introduced in Sect. "A simplistic view of
pressure." This will be shown by presenting a more sophisticated
version of the derivation presented there.

First, the impingement rate (Zw) will be calculated, which is defned as

the number of particles colliding into the unit area of the wall in unit
time. Similarly to Fig. 1, we will consider a fat area of the wall with
surface A and a time interval Δt, in which we count the collisions.
Consider a box of base A and very small thickness dx at a distance x
from the wall as depicted in Fig. 5. The volume of this box is Adx, the
number of particles in it is cAdx. Some of these particles collide with
the wall within time Δt. To do this, the velocity component of the
particle in direction x must be larger than x/Δt. The cumulative
distribution helps identify how many of the particles satisfy this
criterion: (1−F(x/Δt))cAdx.
With the previous sequence of thought, we counted only those particles
that are at a distance of x from the wall and will collide with it within
the time interval of Δt. To obtain the total number, we must consider
all the possible values of x and sum up the individual contributions
from the collection of very thin boxes. This is what integration does.
Once we are done with the summation, we should divide by the surface
area A and time interval Δt. Overall, the following formula is obtained:
Fig. 5 A sketch for calculating
effusion rate and pressure

The last part of Eq. 37 is the classical formula for impingement rate,
indeed (p. 711 in [8], but named ‘collision fux’ there).
There are two integrations in this formula. The inner one (ending in
dvx) calculates the number of species that show vx≥x/Δt at a fxed
distance of x from the wall (the ones which will collide within a time
interval of Δt), whereas the outer integration (ending in dx) sums up
the contributions from all particles at any distance x from the wall.

A slight modification of Eq. 37 yields the pressure exerted on surface

A. The only difference is that we need to sum the momentum change
(2mvx) rather than the number of colliding particles.

This derivation gave the ideal gas law in a form that was
already shown in Eq. 3.

The transformations in Eq. 38 are the closest we can go to a general

theoretical proof of the ideal gas law. We can select a very small, fat
surface on the wall of the container, even if it is generally curved. The
distribution of the velocity component of the particle perpendicular to
this surface does not depend on the direction; it is always given by
Eq. 32. If some worries arise because the container might not be very
large in this direction, then the time interval Δt can be shortened; the
results do not depend on its value.

The knowledge of the probability density function opens the door to

calculating various averages through integration. For example, the
arithmetic mean of the velocity in direction x is obtained as follows:

As already explained, this arithmetic mean is 0 as the distribution is

symmetric: the same velocity is equally likely in the positive and
negative direction. The idea of using the mean velocity of the particle
moving in the positive direction was brought up there as well. This
could be given by the following integral:

Note that the multiplier 2 is necessary here because the density

function f(vx) gives 1 as an integral between−∞ and+∞. This integral
between the limits 0 and +∞ is only 0.5 (again, the distribution is
symmetric); hence, the need for the factor of 2. The final result in
Eq. 40 shows that it contains the constant π, so it would not be fruitful
to use this quantity in an attempted derivation of the ideal gas.
By an analogous integration, the arithmetic mean of the square of the
velocities can also be computed:

Compare this result with the simplistic derivation of pressure in Sect.

"A simplistic view of pressure." It is seen that replacing vx 2 by <vx
2>in Eq. 7 would also give an acceptable derivation of the ideal gas law.
Note that, in Sect. "A simplistic view of pressure", a value for vx 2 was
obtained from the average energy given by the equipartition theorem.
It means that introducing kinetic energy instead of velocity in the
distribution leads to further insight. As only movement in direction x
is considered, the kinetic energy associated with the motion in this
direction should be considered:

A very nice property of cumulative distribution functions is that they

give probabilities as values, so one can change the independent
variables in them at will. The same is not true for probability density
functions, which have physical dimensions. When we wish to switch
from using vx to Ex in Eq. 31, it must be remembered that vx can be
positive and negative as well. In addition, vx and −vx give the same
value of Ex, which is always positive. The symmetry of the distribution
F(vx) provides an easy way to write F(Ex):

As in the previous case, the probability density function is obtained by

derivation:

The shapes of these two energy distributions are shown in Figs. S1 and
S2 in the Supplementary Information. The arithmetic mean of the
energy can be calculated in a way that is fully analogous with the one
shown for Eq. 39:
This formula verifies that the velocity component and energy
distributions obtained here are in agreement with the equipartition
theorem. Furthermore, a comparison of Eqs. 41 and 45 uncovers the
following relation, which may be unsurprising but still notable:

The arithmetic mean for the relative velocity components is expected

to be zero, which is verified by the usual calculation:

The arithmetic mean for the square of the relative velocity components
turns out to be twice the value calculated for the analogous quantity
measured in the other coordinate system:

A further interesting use of this formula is in the calculation of energy

from the relative velocity component:

Speed distribution

Now, we can turn our attention to the speed of the particles. The
distributions of the velocity components are already known; so is
Eq. 4, which connects them to speed. From a probability theory view,
what needs to be calculated is the square root of the sum of the squares
of three identical, independent normal distributions. Fortunately, this
distribution is known on its own right; it is called chi distribution with
three degrees of freedom. The easiest way to discover this is simply to
read a good textbook on probability theory. Going into details about
the derivation and properties of this distribution would lead too far
into the kingdom of mathematics, but one sequence of thought will be
shown here. To fnd a formula for the speed distribution, we should
remember that such changes on independent variables are best
attempted using the cumulative distribution function. To obtain the
probability that the speed of a particle is smaller than s, we need to add
the product of probability densities f(vx), f(vy) and f(vz) for all velocity
vectors for which vx 2+vy 2+vz 2

Thermodynamics of ideal gases and various equations

of state

One of the central issues in the kinetic molecular theory for ideal gases
was the (average) kinetic energy of gas particles. Therefore, it is natural
to seek connections with the classical thermodynamic functions such
as internal energy, enthalpy and entropy [23, 24]. As the frst law of
thermodynamics makes a statement about internal energy, it is the
logical beginning of the discussion. We will keep our earlier stated
preference for intensive physical properties, so molar internal energy
(Um) will be used. The temperature dependence of this quantity at
constant molar volume is described by an important derivative called
molar heat capacity (CV,m):

The most common defnition would be to use extensive internal energy

and volume in this formula: indeed, this is done in most textbooks.
Unfortunately, from a purely mathematical point of view, that practice
is slightly sloppy because it assumes that amounts of substances do not
change (i.e., the system is closed) but seldom states explicitly so. For
example, the extensive heat capacity (CV) should have the more
rigorous defnition as follows:

Then, one could obtain CV,m as the ratio of CV and n. The assumption
of a closed system is not always necessary for the common equations
used in thermodynamics; some of them are valid for open systems as
well. The otherwise necessary care about the amounts of substances in
relation to other extensive quantities only appears in textbooks when
the discussion of chemical potentials begins. To avoid these problems,
this text will keep sticking to the use of intensive quantities
consistently.

Unfortunately, CV,m is not specifed by the fact that a gas follows ideal
behavior. It is not only that a value is not provided for CV,m, but it is
not even necessarily independent of temperature! This is an important
point: many formulas found in textbooks for the thermodynamics of
ideal gases tacitly assume a temperature-independent CV,m, which
may sometimes be a source of confusion. In this text, we will deal frst
with some cases where this assumption is not necessary. It is usually
advantageous to consider molar internal energy as a function of
temperature and molar volume. This is simply a matter of selection:
Gibbs’ phase rule ensures that giving two of the properties of a one-
component, onephase system defnes all others. In this case, the most
common choice is out of pure convenience: formulas tend to be
reasonably simple with this selection.

Conclusion and outlook

The most important aspect that needs to be recapitulated at the end of
the article is that the concept ‘ideal gas’ refers to a state that is available
under certain conditions (pressure, temperature) for most of the
materials. Even if organic molecules decompose with an increase in
temperature, decreasing the pressure without heating could in theory
be used. No substance can be declared to be an ideal gas without
specifying these conditions. The second important fact to be recalled is
that the commonly used form of the ideal gas law does not contain any
constants that depend on the chemical identity of the gas, yet most of
the properties of a sample following ideal gas behavior are still
dependent on what the material is.

Physical properties discussed in this article have been intentionally

restricted to those that can be interpreted based on the view that the
particles of an ideal gas are mass points. There are some quantities for
which it is essential to consider the size of the molecules: a non-
exhaustive list of examples includes frequency of intermolecular
collisions, free mean path, difusion constant and viscosity. The
consistent interpretation of these properties for ideal gases raises a
number of further specifc problems, which will be discussed in a
forthcoming article.

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