Inconsistencies in The Boltzmann-Gibbs Energy Distribution

Vol.
6, 2021-17
Inconsistencies in the Boltzmann-Gibbs Energy Distribution
Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi: 10.13140/RG.2.2.10772.42887
Abstract
The Boltzmann-Gibbs energy distribution is one of the cornerstones of modern statistical

mechanics and thermodynamics. According to this distribution, the energy of a molecular
system follows an exponential probability model. However, in this report the validity of the
Boltzmann-Gibbs energy distribution is questioned since different mathematical
inconsistencies are observed. As a result, the Boltzmann distribution of molecular kinetic
energy should be replaced by a Chi-squared distribution with 3 degrees of freedom (for
monoatomic ideal gases). Similarly, the Gibbs distribution of energy for a system of size N
should be replaced by a Chi-squared distribution with 3N degrees of freedom, for monoatomic
ideal gases. The proposed distributions are shown to be mathematically consistent, where the
Boltzmann-Gibbs distribution fails.
Keywords
Boltzmann Distribution, Energy, Kinetic Energy, Gibbs Distribution, Maxwell-Boltzmann

Distribution, Molecular Energy, Probability, Statistical Mechanics, Statistical Thermodynamics.
1. Introduction
In 1877, Ludwig Boltzmann gracefully derived and found the most probable distribution of
energy in a molecular system at thermal equilibrium [1]. This landmark work has been recently
reprinted and translated into English for easier access [2,3]. Boltzmann considered an
ensemble of possible systems with the same number of molecules ( ) and the same total
kinetic energy ( ). He considered energy to be quantized into packets of energy , and
then considered all possible combinations of discrete numbers of packets into the molecules
available. Mathematically, he finds that the equilibrium distribution, as the most probable
distribution of molecular energy ( ) in the system for , is:
18/11/2021 ForsChem Research Reports Vol. 6, 2021-17 (1 / 26)

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Inconsistencies in the Boltzmann-Gibbs
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( )
(1.1)
where is the average kinetic energy of a molecule, and is a probability value.
His derivation was also extended to continuum energy systems. A simple extension of Eq. (1.1)
can be obtained by considering , where is the continuous kinetic energy of a
molecule. Thus,
( ) ( )
(1.2)
where is the probability density function of the energy distribution, and therefore:
( )
(1.3)
which simply represents a continuous exponential distribution model [4].
In 1902, Josiah Willard Gibbs extensively used the exponential distribution in his development
of statistical mechanics [5]. While Gibbs was aware of Boltzmann’s works on the distribution of
energy, he presented a different (although less rigorous) derivation. First, he stated the
statistical equilibrium of a molecular system as follows§:
∑( )
(1.4)
where is the probability density function** of the energy ( ), and and are the momenta
and position coordinates of each molecule. He then expressed Eq. (1.4) as follows††:
∑( )
(1.5)
In addition, should also satisfy:
§
The original mathematical notation used by Gibbs did not distinguish partial from total derivatives.
**
Gibbs denoted this term as the coefficient of probability, or the quotient of the density-in-phase by the
whole number of systems.
††
Assuming ∑ ( ), then , and .

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∫ ∫ ( )
(1.6)
Eq. (1.6) shows that is actually a joint probability density function.
Now, considering the “most simple case conceivable” (i.e. apparently using the Principle of
Parsimony [6]), Gibbs concluded that the energy distribution function should be:
( )
(1.7)
where and are constants. This exponential function is similar to the function obtained
by Boltzmann, and has been considered to be basically the same, and for this reason, the
distribution is usually denoted as the Boltzmann-Gibbs distribution [7].
By comparing the results obtained by statistical mechanics for an ensemble using the
Boltzmann-Gibbs distribution, and the equations of classical thermodynamics, it is possible to
conclude that [8], where is the Boltzmann constant, represents the temperature
of the system, the number of molecules, and the volume of the system. Therefore the
probability ( ) of finding a system of energy in an ensemble is [9]:
( )
(1.8)
The Boltzmann-Gibbs distribution has been one of the cornerstones of statistical

thermodynamics and has also found application in other fields such as economics [10] and
machine learning [11], just to mention a few.
However, it must also be mentioned that certain inconsistencies are present in both the
derivation and the interpretation of the Boltzmann-Gauss distribution of energy. The most
relevant inconsistencies of the Boltzmann-Gibbs distribution will be explained in Section 2. A
proposed correction considering the energy distribution of monoatomic ideal gases will be
introduced in Section 3.

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2. Inconsistencies in the Boltzmann-Gibbs Distribution
2.1. Boltzmann’s Energy is different from Gibbs’ Energy
First of all, let us state the fact that the Boltzmann and Gibbs distributions of energy, while
mathematically similar, are not exactly the same because they represent different variables. In
the case of Boltzmann distribution, we have the distribution of the kinetic energy of individual
molecules ( ) in a system at constant temperature (and total kinetic energy). In the case of
Gibbs distribution, we have the distribution of total energy ( ) of individual systems in a
canonical NVT ensemble of molecular systems. This can be clearly evidenced in their original
texts [1,5]. This might also be the reason why Gibbs did not mention Boltzmann in the
derivation of his distribution. From now on, we will refer to each distribution independently.
In mathematical terms, the energy discussed by Gibbs ( ) can be related to the energy
discussed by Boltzmann ( ) by means of the following expression‡‡:
∑( ( ))
(2.1)
So, formally speaking, the probability density of the total energy of the system is (considering
the change of variable theorem [12]):
∑ ∑ ∑
( ) ∫ ∫ ∫ ∫ ∏( ) ∏( )
( ∑ ∑ ( ))
(2.2)
Now, assuming that all molecules have identical probability distributions, corresponding to
Boltzmann’s distribution of molecular kinetic energy, then we obtain:
( ∑ ) ∑ ( )
( ) ∫ ∫ ∏( )
( )
(2.3)
‡‡
By assuming the submolecular internal energy to remain constant, it can be neglected from this
analysis.

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where , and is the internal energy of the ensemble. Therefore:
∑ ( )
( ) ∫ ∫ ∏( )
( )
(2.4)
So, up to this point, the distribution of total energy in the ensemble depends on the particular
distribution of potential energies for each molecule ( ).
Simply assuming an ideal gas, where ( ) , we get:
( )
( )
(2.5)
Since is a constant in an ensemble, and the following properties must hold for the
probability density function:
∫ ( )
(2.6)
∫ ( ) 〈 〉
(2.7)
then, we can obtain the implicit conditions for the permissible limits of the distribution:
( ) ( ) ( )
(2.8)
( ) ( )
(2.9)
where ( ) represents the incomplete gamma function and ! is the factorial operator.
Eq. (2.5) obtained from the Boltzmann distribution of molecular kinetic energies in ideal gases,
can be considered equivalent to Gibbs distribution of total energy (Eq. 1.7) only if:
(2.10)
( ) ( )
(2.11)

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However, this implies that the parameter is not a constant but a function of (except for
), and this is inconsistent with Gibbs distribution.
The case when is interesting, because the total energy distribution becomes:
( )
(2.12)
which corresponds to the Boltzmann distribution.
In other words, the Gibbs distribution would correspond to the Boltzmann distribution only
when we consider unimolecular systems ( ). This makes sense because only then, the
molecular kinetic energy corresponds to the total energy of the system.
2.2. The Boltzmann and Gibbs Distributions are only valid for Kinetic Energies
Boltzmann derived the energy distribution considering only kinetic energies, as it is clearly
expressed in his derivation [1-3]. He did not consider potential energy terms.
On the other hand, Gibbs considered the total energy of the system including both kinetic and
potential energy terms. By observing Eq. (1.7) one may conclude that the model obtained by
Gibbs can be considered as an exponential distribution with a location shift. Thus, the term in
Eq. (1.7) can be used to guarantee that the value remains always negative. Thus, the
following condition must be satisfied:
(2.13)
where is the minimum total potential energy in the system, and it can be negative.
Now, the probability density function of the total energy must also satisfy the following
condition:
∫ ( ) ∫
(2.14)
From which the following relation is obtained (assuming and as constants):
(2.15)
Assuming , then

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(2.16)
satisfying condition (2.13).
Gibbs probability density function then becomes:
( )
(2.17)
with an average total energy given by:
〈 〉 ∫ ∫
(2.18)
According to Boltzmann’s interpretation of the exponential distribution (cf. Eq. 1.3), the term
represents the average thermal (kinetic) energy of the system and so, we may conclude that
the average potential energy of the system is:
〈 〉 〈 〉
(2.19)
In other words, the total potential energy is constant for all the systems in the ensemble.
Unfortunately, this is only possible in the case of ideal gases, where 〈 〉 .
For this reason, we can see that even for the Gibbs distribution, only kinetic energies can be
considered.
2.3. The Boltzmann and Gibbs Distributions are not consistent with the Maxwell-Boltzmann
Distribution
Maxwell [13] and Boltzmann [14] suggested that the molecular velocities in any arbitrary
direction become normally distributed due to the frequent exchange of kinetic energy and
momentum as a result of molecular collisions. The probability density function of the molecular
velocity ( ) in an arbitrary direction ( ) can be expressed as follows:
( ) √
(2.20)

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where is the mass of the molecule considered, and is the temperature of the molecular
system. Eq. (2.20) implies that the average molecular velocity is always zero, because it is
always considered relative to the velocity of the system. They also assumed that for isotropic
systems the distribution is identical for any arbitrary direction selected ( , or ).
Assuming this distribution of molecular velocities, the translational kinetic energy of a single
molecule will be given by:
( )
(2.21)
Using the change of variable theorem [12], the following distribution of molecular kinetic
energy is obtained [15]:
( ) √
( )
(2.22)
corresponding to a distribution (with degrees of freedom, one for each orthogonal

direction).
While Eq. (2.22) shows certain similarities with Eq. (1.3), they are clearly different functions.
Therefore, the Boltzmann distribution of molecular kinetic energies is inconsistent with the
Maxwell-Boltzmann distribution of molecular velocities.
In addition, considering the distribution given by Eq. (2.22) and using the change of variable
theorem for the total energy of the system (Eq. 2.1), we obtain (from Eq. 2.2):
∑ ∑ ∑
( √ )
( ) ∫ ∫ ∫ ∫ ∏( )
( )
∑ ( )
∏( ) √ ∑ ∑ ( )
( √ ) ( ) ∑ ( )
∫ ∫ ∏( )
( ) ( )
(2.23)
For a monoatomic ideal gas system, Eq. (2.23) simplifies into:

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( )
( )
( ) ( ) ( )
(2.24)
Eq. (2.24) simply indicates that the term behaves as a random variable with degrees
of freedom. Despite the fact that the exponential term in Eq. (2.24) is similar to the modern
interpretation of the energy distribution (Eq. 1.8), this result is clearly different from Gibbs’
exponential probability distribution. Therefore, Gibbs’ energy distribution is also inconsistent
with the Maxwell-Boltzmann distribution of molecular velocities.
2.4. The Boltzmann and Gibbs Distributions are not consistent for 3-Dimensional Systems
Let us now consider the modern interpretation of the Boltzmann-Gibbs distribution. The
probability density function of the total energy of the system is given by (from Eq. 1.8)§§:
( )
(2.25)
Then, the average energy of the ensemble ( ) will be given by:
(2.26)
On the other hand, we know that the internal energy of an ideal gas system composed of
monoatomic molecules is [9]:
(2.27)
Even if Eq. (2.26) is assumed to represent the molar internal energy of the system, the result
obtained would only be consistent with an ideal monoatomic gas in dimensions.
If we consider the original expression obtained by Boltzmann for the molecular kinetic energy
(Eq. 1.3), then by using Eq. (2.27) we obtain for monoatomic ideal gases in dimensions:
§§
This is the only expression that can be obtained from ( ) , also resulting in a
consistent probability density function (∫ ).

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( )
(2.28)
which is also different from Eq. (2.25).
In any case, we can observe that the modern interpretation of the Boltzmann and Gibbs
distributions of energy is not consistent with the total energy of -dimensional monoatomic
ideal gases, and much less with non-ideal gases or condensed systems.
2.5. The Gibbs Distribution is not consistent with the Zeroth Law of Thermodynamics
Let us consider two systems and , both at thermal equilibrium at the same temperature .
System has a total energy , whereas system has a total energy . Then, both systems
are mixed forming a new system of total energy
(2.29)
which is also at thermal equilibrium at the same temperature .
Since the systems are at equilibrium, let us assume that the total energies of the systems are
described by the Gibbs distribution functions (Eq. 2.25):
( )
(2.30)
( )
(2.31)
( )
(2.32)
However, we can also determine the probability density function of system by applying the
change of variable theorem to Eq. (2.29):
( ) ∫ ( ) ( ) ∫
( ) ( )
(2.33)

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But then, Eq. (2.32) is different than Eq. (2.33). If we assume that the distribution at equilibrium
is the Gibbs distribution, and then this result indicates that the addition of two systems at
thermal equilibrium does not result in a system at thermal equilibrium (as expected by the
zeroth law of thermodynamics [16]). Therefore, the Gibbs distribution is not consistent with the
zeroth-law of thermodynamics.
An alternative derivation of the Gibbs distribution for this situation can be found in the
literature [9], and it will be explained and discussed as follows.
The probability of having a system with energy is the joint probability of each individual,
independent system:
( ) ( ) ( ) ( )
(2.34)
Differentiating this expression with respect to we obtain:
( )
( ( ) ( )) ( ( ) ( ))
( ) ( ) ( )
( )
( )
(2.35)
An alternative result can be obtained considering instead of :
( ) ( )
( )
( )
(2.36)
These expressions can be combined to yield:
( ) ( )
( ) ( )
(2.37)
where is a positive constant.
Integrating we obtain the Gibbs distribution:
( )
(2.38)
( )
(2.39)

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While the mathematics of this derivation seems correct, there is a problem with the
interpretation of the probabilities in Eq. (2.34) that makes it invalid.
First of all, if we know the values of both energies and , then the probability described by
Eq. (2.34) is actually the conditional probability ( ). If that is the case, the
differentials in Eq. (2.35) are zero because and must be treated as constants. Therefore,
, and the solution is actually undetermined.
If we know energy , but energy is unknown (is a variable), then we have:
( ) ( ) ( )
(2.40)
Since is a constant, the differential becomes:
( ) ( ) ( )
( )
( )
(2.41)
but
( ) ( )
( ) ( )
(2.42)
( )
because is undetermined (since both ( ) and are constants). Thus, nothing can
be concluded about the probability function. A similar conclusion is obtained if energy is
constant but energy is variable.
Finally, if both energies are unknown or variable, then Eq. (2.34) is not valid, because the term
( ) must consider all possible values of and whose sum result in :
( ) ∑ ( ) ( )
(2.43)
Since energy can be considered as a continuous variable, Eq. (2.43) is better represented by an
integral in terms of the probability density functions. Such integral is equivalently obtained by
applying the change of variable theorem [12], which is the correct approach for this analysis.
In fact, if we consider the distribution of the total kinetic energy for monoatomic ideal
gases given by Eq. (2.24), we obtain the following individual distributions of systems , and
:

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( )
( )
( )
(2.44)
( )
( )
( )
(2.45)
( )
( )
( )
(2.46)
Again, determining the probability density function of system by applying the change of
variable theorem to Eq. (2.29), we obtain:
( ) ∫ ( ) ( )
∫ ( ) ( )
( ) ( )( )
( )
( )
∫ ( ) ( ) ( )
( ) ( )( )
( ) ( ) ( ) ( )
( ) ( ) ( ( ) ) ( )
(2.47)
which is equivalent to Eq. (2.46), confirming the validity of the zeroth law of thermodynamics
when the Maxwell-Boltzmann distribution of molecular velocities is considered.
2.6. The Boltzmann and Gibbs Distributions are not necessarily Conditions for Equilibrium
The most important premise of the Boltzmann and Gibbs distributions is that the system
considered is at equilibrium. Let us discuss this premise for each case separately.
In the case of Boltzmann’s derivation, as described in Section 1, a certain kinetic energy

is distributed between different molecules. Boltzmann determines the exponential
distribution as the most probable random distribution of kinetic energy between the

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molecules. From the ergodic hypothesis [17] we can assume that the most probable
distribution corresponds to the equilibrium distribution. We can imagine a similar situation
when each coin from a certain pool of coins ( ) is randomly distributed among different
people. The implicit assumption here is that each coin or packet of energy ( ) is randomly
assigned to each person or molecule, respectively.
However, the kinetic energy in a molecular system is not assigned packet by packet
independently, but it is the result of kinetic energy exchange between molecules during
collisions. In other words, the kinetic energy distribution is constrained by the energy exchange
taking place as a result of molecular collisions.
Assuming elastic collisions, we can find the following general expression for the molecular
velocities after collision considering the conservation of momentum and translational kinetic
energy [18]:
( )
( ( ( ) ( )) ( ( ) ( ))
( ( ) ( )))
(2.48)
where and are two different molecules with masses and , respectively; and are
collision angles describing the position of the molecules at collision with respect to the
arbitrary coordinate system ( , ); and ( ) is the velocity of
molecule in the -direction before the collision. Similar expressions can be obtained for all
orthogonal directions.
After multiple ( ) collisions, the velocity of molecule in the -direction can be described by
the following expression:
( ) ( )
∑ ( )
( ( ( ) ( ))
( ( ) ( ))
( ( ) ( )))
(2.49)

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Now, the equilibrium distribution of molecular velocities is obtained when
( )( ) ( )( )
(2.50)
Assuming that the equilibrium distribution has been achieved after the -th collision ( ),
then additional collisions will preserve the equilibrium distribution, independently of the
number of collisions taking place. Also assuming an invariant distribution of molecular masses
and uniform distributions of collision angles, then the distribution of will also remain
invariant. Now, since the number of collisions can be quite large and the distribution of is
constant, due to the Central Limit Theorem [19] the equilibrium distribution of molecular
velocities must necessarily be normal.
In other words, the Maxwell-Boltzmann distribution can be considered as generally valid [16],
and therefore, the distribution of molecular kinetic energy is a distribution (with degrees
***
of freedom) and not an exponential distribution such as the Boltzmann distribution.
The mandatory question now is what was wrong with Boltzmann derivation? As it was
previously mentioned, his analysis was based on an unconstrained system. But due to the
limitations in kinetic energy exchange, and the -dimensional nature of the molecular kinetic
energy, the unconstrained solution is not necessarily valid. In fact, let us determine equilibrium
distribution of molecular velocities in a single direction assuming Boltzmann distribution to be
valid. Using the change of variable theorem [12]:
( ) ∫ ∫ ( ) ( ) ( )
∫ ( ) ∫ ( )
(2.51)
Each remaining integral corresponds to the expected value of the corresponding exponential
function, and is a constant value ( ) because it is a definite integral:
∫ ( ) ( )
(2.52)
***
Please notice that the exponential distribution corresponds to a distribution (with degrees of
freedom). Thus, the exponential distribution would be valid only for the molecular kinetic energy in -
dimensional systems.

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where ( ) is the expected value operator (not to be misinterpreted as an energy term).
Now, assuming that the velocity distribution is identical in all directions:
( )
(2.53)
The consistency of this probability density function requires:
∫ ∫
(2.54)
and therefore the constant value must satisfy:
(2.55)
Using this value, the expected value of the exponential term evaluated for is:
( ) ∫ ∫
(2.56)
Since the constant found for is different from the constant found for all other velocity
components, we can conclude that there is no velocity distribution giving rise to an exponential
distribution of the kinetic energy in a -dimensional system. This can also be confirmed by the
fact that ( ) is only possible if for all molecules in the system. Then, the total
kinetic energy of the system would be constant and zero.
In the case of Gibbs’ derivation, let us recall the equilibrium expression that he obtained (Eq.
1.5):
∑( )
(2.57)
If we consider the following equivalences given by the chain rule:
(2.58)

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(2.59)
then we obtain:
∑( )
(2.60)
which is valid for any function . Thus, Gibbs’ equilibrium expression cannot actually be used to
obtain the distribution of energy at equilibrium.
3. Proposed Energy Distribution Model for Monoatomic Ideal Gases
In this section, the proposed corrected energy distribution model is presented for the simplest
case of monoatomic ideal gases. A more general expression considering other molecular
systems will be presented in an upcoming report. In the case of monoatomic ideal gases, only
the translational kinetic energy of the molecules is considered.
3.1. Translational Molecular Kinetic Energy Distribution
The distribution of translational molecular kinetic energy has been already previously derived
(Section 2.3 and Ref. [15]). Assuming that at equilibrium the molecular velocities in each
direction are normally distributed (Maxwell-Boltzmann model), then we obtain the following
distribution for the translational kinetic energy (Eq. 2.22):
( ) √
√
(3.1)
where represents the translational kinetic energy of each molecule, and is the overall
system temperature.
Eq. (3.1) is a model simplification for the distribution of energy because real molecular velocities
are finite, and the truncated distribution results in a different mathematical expression.
However, for real molecular systems, the truncated distributions are adequately approximated
by the corresponding unbounded models [20].

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For example, considering molecular velocity limits we may find a maximum translational kinetic
energy limiting the distribution of energy. Thus, the truncated energy distribution
becomes:
( ) √
√
( )
(3.2)
where ( ) represents the incomplete gamma function.
If we consider a maximum molecular speed of 〈 〉 [20], where 〈 〉 √ is the
average molecular speed, then , and ( ) ( )

Thus, it can be concluded that Eq. (3.1) is an adequate approximation of the
translational kinetic energy distribution of the molecules.
Figure 1 shows the typical behavior of the molecular kinetic energy distribution given in Eq.
(3.1), compared to the behavior described by the Boltzmann distribution (Eq. 1.3).
Figure 1. Comparison of models of molecular kinetic energy distribution. Solid blue line:
distribution (Eq. 3.1). Dashed red line: Boltzmann exponential distribution (Eq. 1.3).

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3.2. Total System Energy Distribution
Using Eq. (3.1), the total energy of a molecular system becomes (considering only the
translational molecular kinetic energy):
(3.3)
Using the change of variable theorem [12] we obtain (c.f. Eq. 2.24 derived in Section 2.3):
( )
( )
( )
(3.4)
Again, we may find Eq. (3.4) to be a good approximation of the truncated distribution for
, particularly for large systems.
Figure 2. Kinetic energy distribution of a molecular system for different system sizes (
). All curves are obtained using the distribution (Eq. 3.4).

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Figure 2 shows the behavior of the energy distribution given in Eq. (3.4) for different system
sizes. For unimolecular systems, the molecular kinetic energy distribution is obtained (Eq. 3.1).
As the system size increases, a normal distribution of system energy is obtained. Such normal
behavior is obtained even for molecules. As the molecular size increases further, the
distribution approaches a Dirac distribution:
( )
( ) {
(3.5)
As a comparison, the behavior of the Gibbs distribution (Eq. 2.25) for different system sizes is
presented in Figure 3. The energy distribution remains exponential independently of the
system size. It never behaves normally, but as the system size increases, it seems to behave as
the following Dirac distribution:
( ) ( ) {
(3.6)
Figure 3. Gibbs energy distribution (Eq. 2.25) of a molecular system for different system sizes
( ).

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According to the Gibbs distribution, the most probable energy value of the system is always
zero, while for large systems the expected energy value is also zero. This, again, is inconsistent
with the expected energy value of , which is precisely the result obtained in Eq. (3.5) for
the distribution.
3.3. Most Probable Distribution
A simple visual inspection of Eq. (3.1) and (3.4) compared to Eq. (1.3) and (1.7) shows that the
exponential term remains as a common factor. However, the distributions obtained from the
Maxwell-Boltzmann assumption ( distributions) lead to variable pre-exponential terms, and
this is an important difference with respect to the simple exponential model.
According to Boltzmann [1], the most probable distribution corresponds to the state
configuration that maximizes the number of permutations ( ) of such state:
(3.7)
where is the number of molecules in the system, is the number of molecules with kinetic
energy , represents a packet of energy, and
(3.8)
Thus, a maximum permutation is obtained by minimizing the denominator in Eq. (3.7), which
can be alternatively expressed for large systems as follows:
∏( ( ) )
(3.9)
where ( ) ( ) , and .
Taking the natural logarithm of Eq. (3.9) and using Stirling’s approximation [21] we obtain:

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( )
( )
∑ (( ( ) )) ∑ (√ ( ) ( ) )
∑[ ( ( ) )( ( ( ) ) )]
(3.10)
This expression can be transformed into an integral assuming . Also considering

that the following relationship holds: ( ), the resulting expression is:
∑ (( ( ) )) ∫[ ( ( ) )( ( ( ) ) )] ∫ ( ( ) )
(∫ ( ) ∫ ( ( )) ) ( ) ∫ ( ( ))
(3.11)
Thus, the most probable distribution is obtained by solving the following minimization
problem:
∫ ( ( ))
(3.12)
Using Boltzmann exponential distribution (Eq. 1.3) we obtain:
∫ ( ( )) ∫ ( ) ∫[ ( ) ] [ ( ) ]
[ ( ) ]
(3.13)
since .
On the other hand, using the distribution (Eq. 3.1) the objective function is:

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∫ ( ( )) ∫ ( √ ) ∫[ ( ) ( ) ]
√ √
√
( ) ( ( ) )
(3.14)
Now, since the average molecular kinetic energy is:
(3.15)
Then, Eq. (3.14) can be expressed as:
√
∫ ( ( )) [ ( ) ( ( )) ]
√
[ ( ) ( ) ( ) ]
[ ( ) (√ ) (√ ) ]
(3.16)
The lowest integral value between both distributions is the most probable distribution.
The value of the integral of the logarithm of the distribution given in Eq. (3.16) is less than
the integral of the logarithm of the exponential distribution given in Eq. (3.13) when:
(√ ) (√ )
(3.17)
This expression is negative only for or . For any other natural value, and
particularly for , the objective function of the distribution is better (less) than the
objective function of the exponential distribution. So, we can conclude that in general, the
distribution is more probable than the exponential distribution, considering Boltzmann’s
original criterion (maximization of the number of permutations given in Eq. 3.7).

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4. Conclusion
Different inconsistencies have been found in the Boltzmann-Gibbs exponential distribution of

energy, including:
 The energy considered in Boltzmann distribution is a molecular kinetic energy, whereas

the energy considered in Gibbs distribution is a total energy in an ensemble of NVT
systems. Thus, they are two conceptually different distributions.
 The Boltzmann and Gibbs distributions are only valid for kinetic energies (positive
energies). Potential energies, which may have negative values, cannot be satisfactorily
described by the exponential distribution.
 The Boltzmann and Gibbs exponential distributions of energies are not consistent with
the Maxwell-Boltzmann distribution of molecular velocities. On the other hand, using
the Maxwell-Boltzmann distribution, a distribution with degrees of freedom is
obtained for the molecular kinetic energy, and a distribution with degrees of
freedom is obtained for the total kinetic energy of a system of monoatomic ideal gas
molecules.
 There is no molecular velocity distribution resulting in an exponential distribution of
kinetic energies in dimensional systems. Only when dimensions are considered will
an exponential distribution of energies emerge.
 Gibbs exponential distribution is not consistent with the Zeroth Law of
Thermodynamics. If two systems initially at thermal equilibrium following Gibbs
distribution of energy are mixed, then the resulting system cannot follow Gibbs
distribution of energy. The distribution with degrees of freedom, on the
contrary, satisfies this condition.
 The Boltzmann and Gibbs distributions are not necessarily conditions for equilibrium. In
fact, it can be shown that the distribution is more probable than the exponential
distribution.
 For large systems, the expected energy of the exponential distribution tends to zero,
whereas the expected energy of the distribution satisfactorily tends to the average
energy of the system.
These results indicate that the Boltzmann and Gibbs distributions of energy are not suitable for
describing ideal gas systems in 3 dimensions, and much less, non-ideal gases and condensed
systems. For monoatomic ideal gas systems the distribution satisfactorily describes the
molecular and system kinetic energy, without evident inconsistencies. The energy distribution
considering intermolecular potential energies and submolecular internal energies will be
discussed in a future report. The implication of the inconsistencies in the Boltzmann and Gibbs
distributions on statistical mechanics and thermodynamics, is also an important issue to
explore.

www.forschem.org
Energy Distribution
Hugo Hernandez
ForsChem Research
Acknowledgments
Valuable discussions on this topic with Prof. Jaime Aguirre (Universidad Nacional de Colombia)
are gratefully acknowledged.
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
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mechanischen Wärmetheorie und der Wahrscheinlichkeitsrechnung, respective den Sätzen
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(Abt. II), pp. 373-435.
[2] Hasenöhrl, F. (2012). Wissenschaftliche Abhandlungen. Volume 2: Ludwig Botlzmann.

Cambridge University Press. Chapter 42. pp. 164-223. doi: 10.1017/CBO9781139381437.011.
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Energy Distribution
Hugo Hernandez
ForsChem Research
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Vol.

Inconsistencies in the Boltzmann-Gibbs Energy Distribution

The Boltzmann-Gibbs energy distribution is one of the cornerstones of modern statistical

Boltzmann Distribution, Energy, Kinetic Energy, Gibbs Distribution, Maxwell-Boltzmann

18/11/2021 ForsChem Research Reports Vol. 6, 2021-17 (1 / 26)

In addition, should also satisfy:

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Eq. (1.6) shows that is actually a joint probability density function.

The Boltzmann-Gibbs distribution has been one of the cornerstones of statistical

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2. Inconsistencies in the Boltzmann-Gibbs Distribution

2.1. Boltzmann’s Energy is different from Gibbs’ Energy

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where , and is the internal energy of the ensemble. Therefore:

Simply assuming an ideal gas, where ( ) , we get:

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From which the following relation is obtained (assuming and as constants):

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Gibbs probability density function then becomes:

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corresponding to a distribution (with degrees of freedom, one for each orthogonal

For a monoatomic ideal gas system, Eq. (2.23) simplifies into:

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Then, the average energy of the ensemble ( ) will be given by:

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which is also different from Eq. (2.25).

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Differentiating this expression with respect to we obtain:

Integrating we obtain the Gibbs distribution:

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If we know energy , but energy is unknown (is a variable), then we have:

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In the case of Boltzmann’s derivation, as described in Section 1, a certain kinetic energy

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Now, the equilibrium distribution of molecular velocities is obtained when

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where ( ) is the expected value operator (not to be misinterpreted as an energy term).

Now, assuming that the velocity distribution is identical in all directions:

kinetic energy of the system would be constant and zero.

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3. Proposed Energy Distribution Model for Monoatomic Ideal Gases

3.1. Translational Molecular Kinetic Energy Distribution

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If we consider a maximum molecular speed of 〈 〉 [20], where 〈 〉 √ is the

average molecular speed, then , and ( ) ( )

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3.2. Total System Energy Distribution

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3.3. Most Probable Distribution

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This expression can be transformed into an integral assuming . Also considering

Using Boltzmann exponential distribution (Eq. 1.3) we obtain:

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Now, since the average molecular kinetic energy is:

Then, Eq. (3.14) can be expressed as:

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Different inconsistencies have been found in the Boltzmann-Gibbs exponential distribution of

 The energy considered in Boltzmann distribution is a molecular kinetic energy, whereas

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[2] Hasenöhrl, F. (2012). Wissenschaftliche Abhandlungen. Volume 2: Ludwig Botlzmann.

[4] Exponential distribution. In: Encyclopedia of Mathematics. Springer.