Theory of ideal gas

Zhigang Suo @zhigangsuo

Part of a book on Thermodynamics
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The ideal gas law, PV = NkBT, was discovered empirically over centuries, before the discovery of
entropy.

Wikipedia the empirical discovery of the ideal gas law.

After the discovery of entropy, the ideal gas law is derived from a molecular picture, in just a few
lines. This derivation reveals the molecular origin of the ideal gas law.

Ideal gas law derived 2

Energy of an ideal gas 2
Thermal capacity of an ideal gas 3
Energy transfer by work and by heat 3
Constant-volume process 4
Constant-pressure process 4
Isothermal process 5
Adiabatic process 5
Enthalpy of an ideal gas 6
Entropy of an ideal gas 6
Summary of equations of ideal gas 7
Entropic elasticity 7
Theory of osmosis 8

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Ideal gas law derived
Picture an ideal gas in an experimental setup of a gas, cylinder, piston, weight, and fire. The
piston seals the cylinder, and fixes the number of molecules of the gas in the cylinder, N. The
piston slides relative to the cylinder and changes the volume of the gas, V. The piston slides
with no fiction, so that the weight placed above the cylinder sets the pressure of the gas, P. The
fire outside the cylinder transfers energy by heat to the gas. Denote the temperature of the gas
by T, and the thermal energy of the gas by U.

In an ideal gas, the molecules are far apart on average, so that each molecule can fly anywhere
in the bulb as if all other molecules were absent. Consequently, the number of quantum states
of each molecule is proportional to V, and the number of quantum states of N molecules is
proportional to VN. The proportional factor depends on U and N, but not on V:

Ω(U,V,N) = VNf(U,N),

where f(U,N) stands for a function of U and N, but not V.

The entropy of the gas, S = kB log Ω, is

S(U,V,N) = NkB logV + kB log f(U,N) .

Inserting this expression into an identity in thermodynamics, P/T = ∂S(U,V,N)/∂V, we obtain that

PV = NkBT.

This equation of state is the ideal gas law.

Energy of an ideal gas

Inserting the expression for entropy into the definition of temperature, 1/T = ∂S(U,V,N)/∂U, we
obtain that

1/T = ∂(log f(U,N))/∂U.

This equation shows that T is a function of U and N, and is independent of V. We invert the
function T(U,N) to U(T,N). The thermal energy is an extensive property, proportional to the
number of molecules, N. Write

U = Nu(T).

Here u(T) is the thermal energy per molecule.

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Thermal capacity of an ideal gas
We can specify a state of the gas by a combination of a temperature T and a volume V. For a
general closed system, the pressure is a function of temperature and volume, P(T,V). For an
ideal gas, this function takes the form of the ideal gas law, P = NkBT/V.

For a general closed system, the thermal energy is also a function of temperature and volume,
U(T,V). For an ideal gas, the thermal energy is a function of temperature, and is independent of
volume. The function u(T) is the thermal energy per molecule.

The second equation is also written as

dU = NcV(T)dT.

The function cV(T) = du(T)/dT is the thermal capacity per molecule. We will interpret the
subscript V later. The equation dU = NcV(T)dT fails to obey a rule: whenever temperature is
reported in Kelvin, temperature should appear as kBT. This disobedience results from our
definition of the thermal capacity cV. We define the thermal capacity as the energy per molecule
needed to increase temperature by 1 K, so that cV has the fake unit of J/K.

Thermal capacity per mole or per unit mass is also commonly used. Thermal capacity of an
ideal gas is a function of temperature, cV(T). The function has been determined for many
species of molecules, and is listed in ideal gas tables.

Exercise. In a helium gas, each molecule consists of a single helium atom. For such a gas of
single-atom molecules, the thermal capacity per molecule is cV = 1.5kB, and is independent of
temperature. Calculate the thermal capacity per mole of helium. Calculate the thermal capacity
per unit mass of helium. The molar mass of helium is 4 g/mole.

Energy transfer by work and by heat

The two words, work and heat, are unlikely to be eradicated from thermodynamics soon. We will
have to live with them. So let us know what they are for an ideal gas undergoing a process.

When the volume of the gas changes by dV, the energy transfer by work from the gas to the
surroundings is

dW = PdV.

When the volume of the gas changes by dV and the thermal energy of the gas change by dU,
the energy transfer by heat from the surroundings to the gas is

dQ = NcV(T)dT + PdV.

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Neither the energy transfer by work nor the energy transfer by heat is a function of state; they
depend on process. We next consider several processes.

Constant-volume process
Subject to a constant volume, the gas does no work to the surroundings: dW = 0. Consequently,
the energy transfer by heat equals the change in thermal energy:

dQ = NcV(T)dT.

The quantity cV(T) is the thermal capacity per molecule under constant pressure.

When the temperature changes from T1 to T2, assuming the thermal capacity is independent of
temperature, the energy transfer by heat is

Q = NcV(T2 - T1).

If the thermal capacity is a function of temperature, we calculate the energy transfer by heat by
integration.

Constant-pressure process
Consider the experimental setup of a gas, cylinder, pistorn, and weight. Assume that the weight
placed above the piston is fixed, so that the pressure of the gas is fixed.

For an ideal gas under a constant pressure, the energy transfer by work is

dW = PdV = d(PV) = NkBdT.

For an ideal gas under a constant pressure, the energy transfer by heat is

dQ = N(cV(T) + kB)dT.

The quantity cV(T) + kB is the thermal capacity per molecule under constant pressure, and is
designated as cP(T):

cP(T) = cV(T) + kB.

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Isothermal process
A constant-temperature process is also called an isothermal process. Because of the ideal gas
law, the isothermal process is characterized by a curve PV = constant. Recall the definition of
heat, dQ = dU + dW. For an ideal gas, the isothermal process does not change the thermal
energy, so that the energy transfer by heat to the closed system is the same as the work done
by the closed system:

dW = dQ = (NkBT/V)dV.

When the volume changes from V1 to V2, the energy transfer by heat is

W = Q = NkBT log (V2/V1).

Adiabatic process
In an adiabatic process, no energy transfers by heat between the closed system and the
surroundings, dQ = 0. Thus, dU + PdV = 0. For an ideal gas, this equation becomes

cV(T)dT + (kBT/V)dV = 0.

We further assume that the thermal capacity is independent of temperature. Integration yields

cV log T + kB log V = constant,

or

TVb-1 = constant,

where b = cP/cV. The constant in the above equation is determined by one state in the process,
say the initial state (Ti,Vi). Thus, constant = TiVib-1.

Caution. The result TVb-1 = constant explains adiabatic cooling when a gas expands in an
adiabatic process, and explains adiabatic heating when a gas contracts in an adiabatic process.
The phrase “adiabatic heating” is inconsistent with the definition of the word “heat” in
thermodynamics. In an adiabatic process, a closed system is thermally insulated, and does not
transfer energy by heat. When the volume contracts, the external force does work to the closed
system, so that the thermal energy increases. The word “heating” in the phrase “adiabatic
heating” means increasing thermal energy by work.

Recall the ideal gas law PV = NkBT. The adiabatic process also obeys that

PVb = constant.

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When the volume changes by dV, the adiabatic process transfers energy by work:

dW = PdV = (constant) V-bdV.

Integration yields

W = (constant/(b - 1)) (V1-b+1 - V2-b+1)

Exercise. Assume that an ideal gas has a constant thermal capacity per molecule cV. One mole
of the ideal gas changes from an initial state (Pi,Vi) to a final state (Pf,Vf) along a straight line on
the (P,V) plane. Calculate the energy transfer by work and energy transfer by heat. Calculate the
changes in thermal energy.

Exercise. An ideal gas undergoes an adiabatic process from an initial state (Pi,Vi) to a final state
of volume Vf. Calculate the pressure of the final state, Pf. Calculate the energy transfer by work
in the adiabatic process.

Enthalpy of an ideal gas

Recall the definition of enthalpy of a closed system, H = U + PV. For an ideal gas, PV = NkBT, so
that H = N(u + kBT). The enthalpy per molecule is

h(T) = u(T) + kBT.

Recall the definition of the thermal capacity per molecule under the condition of constant
pressure for a closed system, cP = ∂h(T,P)/∂T. For an ideal gas, we obtain that

cP(T) = cV(T) + kB,

dH = NcP(T)dT.

The ideal gas tables list the functions h(T) and cP(T) for many species of molecules.

Entropy of an ideal gas

Recall the general equation for a closed system

dS = (1/T)dU + (P/T)dV.

Inserting the equations specific to an ideal gas, dU = NcV(T)dT and PV = NkBT, we obtain that

dS = (NcP(T)/T)dT - (NkB/P)dP.

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We have used the relation cP = cV + kB.

Entropy is a function of state. A state of the closed system is specified by two independent
variables, T and P. In the above equation, the first term is due to the change in temperature, and
the second term is due to the change in pressure.

Let T0 be a reference temperature and P0 be a reference pressure. Assume that we know the
absolute entropy at this reference state, S(T0,P0). Given the function cP(T), an integration gives
that

S(T, P) = Ns(T,P0) - NkB log (P/P0).

For many species of molecules, the ideal gas tables list the absolute entropy per molecule,
s(T,P0), at a reference pressure P0, as a function of T. The reference temperature is typically set
as P0 = 100 kPa.

Summary of equations of ideal gas

A state of a pure ideal gas is specified by temperature T and pressure P, along with the number
of molecules N. All the other properties are functions of T, P, N:

V = NkBT/P,
U = Nu(T),
H = Nh(T), h(T) = u(T) + kBT,
S = Ns(T,P0) - NkB log (P/P0).

For many species of molecules, the ideal gas tables list the functions h(T) and s(T,P0).

Exercise. Assume a constant thermal capacity for an ideal gas. Calculate the function S(U,V,N).

Exercise. Use the ideal gas tables to find the energy, enthalpy, and entropy of O2 at 1000 K, 1
MPa.

Exercise. Use the ideal gas tables to find the energy, enthalpy, and entropy of H2O at 1000 K,
100 kPa.

Entropic elasticity
When a spring made of steel is pulled by a force, the spring elongates. When the force is
removed, the spring recovers its initial length. This elasticity is due to a distortion of the electron
cloud of atoms. Such elasticity is called energetic elasticity.

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At a constant temperature, a bag of air acts like a spring. The volume decreases when the
pressure increases, and recovers when the pressure drops. This elasticity clearly does not
result from distortion of electron clouds in the molecules, but from the change of the number of
quantum states with volume. Such elasticity is called entropic elasticity.

Define elastic modulus by

B = - V∂P/∂V.

This definition is incomplete; we need to specify what is taken to be constant when we take the
partial derivative. Let us consider two examples.

Isothermal elastic modulus. Under the isothermal condition, temperature is constant. Recall
the ideal gas law, P = NkBT/V. Taking the partial derivative, we obtain the isothermal elastic
modulus

Bisothermal = P.

Adiabatic elastic modulus. Assume constant thermal capacities, and let b = cP/cV. Under the
adiabatic condition, PVb= constant. Taking the partial derivative, we obtain the adiabatic elastic
modulus

Badibatic = bP.

A gas is stiffer in adiabatic expansion than in isothermal expansion.

Twitter Ideal gas of a single species of molecules

Theory of osmosis
Osmosis. Consider N particles dispersed in a bag of water of volume V. The particles are
different from water molecules, and can be of any size. The particles can be of many species.
When the particles are molecules, we call them solutes. When the particles are somewhat
larger, say from 10 nm to 10 µ m, we call them colloids. The bag is immersed in a tank of pure
water. The bag is made of a semipermeable membrane: water can permeate through the
membrane but the particles cannot.

Osmotic pressure. The physics of this situation is analogous to the ideal gas, provided that the
concentration of the particles is dilute. Every particle is free to explore the entire volume in the
bag. The number of quantum states of the water-particle system scales as

Ω ∝ VN.

As water permeates through the membrane, the volume of the bag V changes.

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Recall S = kB logΩ and the P/T = ∂S(U,V)/∂V, we obtain that

P = kBTN/V.

This pressure is called the osmotic pressure. The ratio N/V is called the concentration of solute.
The law of osmosis is identical to the law of ideal gas.

Balance osmotic pressure by tension. The osmotic pressure can be balanced in several
ways. For example, the tension in the membrane can balance the osmosis pressure. One can
also disperse particles in the tank of water outside the bag. The difference in the concentration
of particles in the bag and that of particles in the tank causes a difference in the pressures in the
bag and in the tank. The difference in pressure can be balanced by the tension in the
membrane. Youtube osmosis (dialysis bag).

Balance osmotic pressure by gravity. As yet another example, we place a rigid,

semi-permeable wall in the liquid, with the particles on one side, but not the other. Water is on
both sides of the wall, but alcohol is only on one side. The molecules of the liquid can diffuse
across the wall, but the particles cannot. For the particles to explore more volume, the liquid
molecules have to diffuse into the side where particles are. If this experiment were carried out in
the zero-gravity environment, the infusion would continue until the pure liquid is depleted. In the
gravitational field, however, the infusion stops when the pressure in the solution balances the
tendency of the infusion. Youtube osmosis (U-tube).

Nobel Lecture. van’t Hoff, Osmotic pressure and chemical equilibrium, 1901.