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Law of Equipartition of Energy

The Law of Equipartition of Energy states that in thermal equilibrium, each degree of freedom of a system contributes an equal amount of energy.

To understand this concept, let's consider a system of particles, such as atoms or molecules, in thermal equilibrium at a given temperature. Each particle in the system has different degrees of freedom, which refer to the different ways it can store and distribute its energy.

According to the Law of Equipartition of Energy, in thermal equilibrium, each degree of freedom of a particle contributes an average energy of (1/2)k_B*T, where k_B is the Boltzmann constant and T is the temperature.

For example, in a monatomic gas (gas consisting of single atoms), each particle has three degrees of freedom associated with its motion in three-dimensional space (one for each spatial dimension). Therefore, each particle in the gas, on average, has an energy of (1/2)k_BT for each degree of freedom, resulting in a total average energy of (3/2)k_BT per particle.

In a diatomic gas, the particles have additional degrees of freedom associated with their rotational and vibrational motion. Each additional degree of freedom contributes an average energy of (1/2)k_BT. Therefore, in addition to the three translational degrees of freedom, a diatomic gas molecule can have additional contributions of (1/2)k_BT for each rotational and vibrational degree of freedom.

The Law of Equipartition of Energy is based on classical statistical mechanics and assumes that the system is in thermal equilibrium and obeys classical behavior. It provides a useful framework for understanding the distribution of energy in different degrees of freedom within a system. However, it may not accurately describe the behavior of quantum systems or systems at very low temperatures where quantum effects dominate.

The Law of Equipartition of Energy can be derived from the principles of classical statistical mechanics and the assumption of thermal equilibrium. Here is a basic proof outline:

Consider a system of N particles in thermal equilibrium at temperature T.


Each particle in the system has multiple degrees of freedom associated with its motion. Let's denote the total number of degrees of freedom as f.


According to classical statistical mechanics, the probability distribution of the system's energy follows the Maxwell-Boltzmann distribution.


The Maxwell-Boltzmann distribution states that the probability of a particle having energy E is given by P(E) = (1/Z) * exp(-E/(k_B*T)), where k_B is the Boltzmann constant and Z is the partition function.


The partition function Z accounts for the sum of probabilities over all possible energy states of the system.


For a system in thermal equilibrium, the average energy 〈E〉 is given by the sum of energy values weighted by their respective probabilities:

〈E〉 = Σ(E * P(E))


Expand the above sum by integrating over all possible energy states:

〈E〉 = ∫(E * P(E)) dE


Substitute P(E) = (1/Z) * exp(-E/(k_B*T)):

〈E〉 = (1/Z) * ∫E * exp(-E/(k_B*T)) dE


Perform the integration and simplify the expression.


Differentiate the average energy 〈E〉 with respect to each degree of freedom. This step involves applying the chain rule and considering the energy expression associated with each degree of freedom.


After differentiation, the resulting average energy per degree of freedom should be (1/2)k_B*T.

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