Plasma Chem Plasma Process (2012) 32:401–407

DOI 10.1007/s11090-012-9356-1

ORIGINAL PAPER

Plasma: The Fourth State of Matter

K. T. A. L. Burm

Received: 14 December 2011 / Accepted: 1 February 2012 / Published online: 17 February 2012
Ó Springer Science+Business Media, LLC 2012

Abstract The plasma state is frequently referred to as the fourth state of matter in the
sequence: solid, liquid, gas, and plasma. The statement implies that plasma is another
phase. Each state is achieved by adding heat to the previous state. The first three states are
the three common phases achieved via phase transitions. The statement that plasmas are
the fourth state of matter is examined considering phase transitions. It is shown that the
transition from gas to plasma is not a phase transition similar to the other phase transitions
at which transitions the differential of the Gibbs free energy equals zero. Therefore, strictly
speaking, plasmas are better not called the fourth state of matter.

Keywords Plasma fundamentals  Plasma thermodynamics  Phase transitions

Introduction

In order to introduce plasmas it is often stated that plasmas are the fourth state of matter in
the sequence: solid, liquid, gas, and plasma [1]. The state of matter changes from solid to
liquid to gas to plasma by increasing the temperature of the material under consideration.
The statement implies that plasma is another phase. In this intuitive approach, plasmas are
often considered the fourth state of matter in popularising scientific books like [2] and web
pages [3, 4] but also in educative books for plasma physics students, such as [5]. The term
state can be used to indicate the appearance of plasma. However, it will be shown that
plasma is not another phase.
A solid changes into a liquid via a first-order phase transition by adding heat to the solid.
A first-order phase transition is a phase transition at which the differential of the Gibbs free
energy equals zero. The liquid changes into a gas by adding heat to the liquid. This occurs
also via a first-order phase transition. The gas changes into a plasma by adding heat to the
gas. This change is however not a first-order phase transition, what will be discussed in
section ‘‘Phase Transitions’’.

K. T. A. L. Burm (&)
PlasmAIX for Plasma Research, Heimerik 47, 2440 Geel, Belgium
e-mail: Karel.Burm@gmx.net

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We will consider in section ‘‘The Helmholtz Free Energy and Plasma’’ the plasma state
as a fourth state which occurs after the other three states, solid, liquid, and gas, at higher
temperatures. By explicitly using the word state and avoiding the word phase, we imply
that the transition from gas to plasma is not required to obey the Clapeyron equation.
However, the comparison still requires that the transition from gas to plasma mimics a
phase transition. The plasma is still considered a numbered state in a not trivial sequence.
The transition from gas to plasma should not differ severely from the transition liquid to
gas.
We will focus in section ‘‘The Helmholtz Free Energy and Plasma’’ on the Helmholtz
free energy F as an alternative for the Gibbs free energy G whose differential equals zero at
a phase transition. If dF = 0 at the transition from gas to plasma, then one might argue that
this transition shows some similarity with the phase transitions between the other states.
We will focus in section ‘‘Plasmas as Gas Mixtures’’ on plasmas as mixtures of mol-
ecules and charged particles. In fact, plasmas are considered to behave as gas mixtures.
The influence of charges is neglected using the quasi-neutrality argument. It is examined
within the framework of plasmas as gas mixtures if the gas to plasma transition can be
considered as a first-order phase transition.
In order to simplify matter, plasmas in full thermal equilibrium will be considered. This
simplification does not influence the conclusions.
The plasmas considered here are quasi-neutral. Not all plasmas are quasi-neutral. An
example is plasma sheaths. Further, macroscopic fields may cause separate transport of
ions and electrons. Notwithstanding that not all plasmas are quasi-neutral, we do not want
to needlessly complicate the discussion.

Phase Transitions

Let us consider a phase transition from phase b to phase a in order to examine the
derivation of the Clapeyron equation and the used assumptions for the phase transitions
between the three phases: solid, liquid, and gas. We are interested in if it is possible to add
plasmas in the derivation.
Phase transitions usually occur at a certain temperature T and at a certain pressure
p. Phase transitions are isobar and isothermal. This makes the thermodynamic state
function G, the Gibbs free energy or the free enthalpy, the ideal function to consider the
phase transition. Note that
G ¼ U þ pV  TS; ð1Þ
with U the internal energy, V the volume, and S the entropy. The differential of G is:
dG ¼ SdT þ Vdp: ð2Þ
For the isothermal and isobar phase transition dG = 0. Indicating the phase with a
superscript and the molar unit with an m subscript, dG = 0 can be written as:

Gam ¼ Gbm : ð3Þ

This relation is valid at (p, T) but also at (p ? dp, T ? dT) such that:

dGam ¼ dGbm ; ð4Þ

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or

Sam dT þ Vma dp ¼ Sbm dT þ Vmb dp: ð5Þ

From the latter expression the relation between pressure and temperature can be deduced,
which is named after Clapeyron:

dp Sa  Sbm
¼ m : ð6Þ
dT Vma  Vmb
Phase transitions occur applying latent heat E to phase b. The accompanied change in
entropy is:
Eba
Sam  Sbm ¼ : ð7Þ
T
The Clapeyron expression becomes [6]:
dp Eba
¼  : ð8Þ
dT Vma  Vmb T

When the a phase is the gas phase, the volume of the higher phase (a) is much larger
than the volume of the lower phase (b), such that Vam - Vbm & Vam. Further, when the a
phase is the gas phase and we assume that the vapour obeys to the gas law, pVm = RT, we
get:
dp Eba dT
¼ : ð9Þ
p R T2
Therefore, the Clapeyron expression is often written as [7]:
  
Eba 1 1
p ¼ p0 exp  ; ð10Þ
R T T0
with p = p0 at T = T0.
In case of a transition from gas to plasma, expression (8) is problematic since Vma 6 Vmb .
Further, it is doubtful that the transition from gas to plasma occurs at constant pressure.
The ion pressure and the electron pressure of the plasma add to the total pressure of the
plasma. And further, the amount of particle increases during the transition from gas to
plasma, something which is not typical for a phase transition.
Therefore, the transition from gas to plasma is not a phase transition similar as the
transition between the three phases: solid, liquid, and gas. The plasma state seems not to be
a different phase following the sequence of the three phases: solid, liquid, and gas.

The Helmholtz Free Energy and Plasma

One might argue that at the transition from gas to plasma, the (atom) temperature and the
volume are constant. Instead of the Gibbs free energy G, the Helmholtz free energy
F seems more appropriate to be considered. Since
dF ¼ SdT  pdV; ð11Þ

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dF = 0 at the transition from gas to plasma. Here, we still neglect the creation of particles.
There are two reasons to do so. First, the electron mass is much lower than the atom and
ion masses such that the contribution of the electrons in the mass density can be neglected.
Second, plasmas are quasi-neutral. This means that the electron density equals the ion
density. The plasma is neutral on a macroscopic scale.
From a similar reasoning as for the Gibbs free energy:

Sam dT  pa dVm ¼ Sbm dT  pb dVm : ð12Þ

The latent heat is now the ionisation energy Eion such that:
dVm Sa  Sbm Eion
¼  ma ¼ a : ð13Þ
dT p  pb ðp  pb ÞT
Note that b is now the gas phase and a the plasma phase. The plasma pressure is
expected to be higher than the gas pressure, such that pa - pb & pa. Further, when we
assume that the plasma obeys to the gas law, pVm = RT, we get:

dVm Eion dT
¼ : ð14Þ
Vm R T2
This expression can be written as:
  
Eion 1 1
Vm ¼ Vm;0 exp  ; ð15Þ
R T T0
with Vm = Vm,0 at T = T0.
Expression (15) makes sense noting that the molar volume decreases with higher
temperatures. Stated otherwise, at higher temperature more ionisation occurs inside a fixed
volume. When the ionisation energy is high, the change in molar volume due to a change in
temperature is larger.
In a microscopic approach, expression (15) becomes the Saha equation for a plasma in
thermal equilibrium [8]. Such microscopic approach should include the various partition
functions through the Helmholtz free energy F and not only the ionisation energy from the
ground state to the first ionisation level Eion.
Expression (15) may be not very useful. Nevertheless, since expression (15) refers to the
Saha equation, it supports the postulations that the (atom) temperature and the volume are
constant during the transition from gas to plasma. This indicates that the transition from gas
to plasma is not only not a first-order phase transition similar as the ones between solid,
liquid, and gas, but also not a higher-order phase transition. The transition from gas to
plasma shows, however, much similarity with the first-order phase transitions of the three
phases solid, liquid, and gas. During phase transitions the volume changes at constant
pressure, while during the creation of plasma the pressure changes at constant volume.

Plasmas as Gas Mixtures

Let us consider plasmas as gases which are ionised. Due to ionisation the gas transits from
a pure gas to a gas with electrons and ions incorporated in it. One may argue that the pure
gas has become a gas mixture.
The thermodynamic state functions H, F, and G include the thermodynamic poten-
tial lj to incorporate changes in the number of particles of species j [9–11]. Let us consider

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an isochoric (dV = 0) and isothermal (dT = 0) process such that the Helmholtz free
energy F is considered. We get
X
dF ¼ SdT  pdV þ lj dNj ; ð16Þ
j¼a;i;e

with Nj the amount of particles (mol or kg) and

 
oF
lj ¼ : ð17Þ
oNj T;V;N6j

The thermodynamic potential l is often called the chemical potential. The thermody-
namic potential can be simplified by noticing that during ionisation an ion and an electron
are created from an atom when applying the ionisation energy Eion. Therefore,
Eion
lj ¼ : ð18Þ
DNj
To simplify the differential of the Helmholtz free energy, we define the ionisation
degree h as:
Ni
h¼ : ð19Þ
Na þ Ni
Our definition focuses on ionisation which is considered as an atom to ion transition.
The differential of the Helmholtz free energy becomes:
DNa DNi DNe
dF ¼ SdT  pdV  Eion þ Eion þ Eion
Na þ Ni Na þ Ni Na þ Ni
¼ SdT  pdV þ Eion dh; ð20Þ

where we normed the created particles on the sum of the number of atoms and ions
(Na ? Ni). This expression is in agreement with literature [12, 13]:

H ¼ U þ pV þ hEion ;
F ¼ U  TS þ hEion ; ð21Þ
G ¼ H  TS þ hEion :
We noticed before that during a phase transition between solid, liquid, and gas, dG = 0.
Let us assume that plasmas can be considered as the fourth state of matter, but now we
include the thermodynamic potential. The inclusion of the thermodynamic potential gives
for dG = 0 or dGam = dGbm (note a is the plasma state and b the gas state):
Sam dT þ Vma dp þ Eion dh ¼ Sbm dT þ Vmb dp: ð22Þ
Since Vam & Vbm,

Sam  Sbm dT ¼ Eion dh: ð23Þ

The difference in entropy can be substituted out similar as in expression (13). This
gives:
dT
dh ¼ ¼ dlnðT Þ; ð24Þ
T

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such that:
 
T
h ¼ h0 þ ln ; ð25Þ
T0
with h = h0 at T = T0.
Expression (25) has no physical meaning. For low temperatures, in case T  T0,
expression (25) gives a negative ionisation degree or h0 must be extremely large. In both
cases expression (25) has no meaning. For high temperatures, in case T ! 1; expression
(25) gives an unlimited high ionisation degree. Again, expression (25) has no meaning.
As stated before, the statement that plasmas can be considered as the fourth state of
matter in the sequence: solid, liquid, gas, and plasma seems to be incorrect.

Discussion

The transition from gas to plasma seems not to occur at constant pressure and at constant
temperature as phase transitions do. The transition from gas to plasma seems to occur at
constant volume. This makes sense since plasmas fill the available space just like gases.
Note however the following: Plasmas are created via ionisation. In order to ionise a
power source is required. Therefore, plasmas fill the available space but disappear without
a nearby power source. Further, very different from gases is that plasmas can be captured
in a magnetic field. The plasma appears only around the magnetic field lines. We may
therefore better state that plasmas fill the available powered space.
Further, it is not obvious that the transition from gas to plasma occurs at constant
temperature. It is expected that the temperature of the atoms in the plasma is roughly equal
to the gas temperature. These particles are not affected by ionisation or any power source.
The charged particles, the ions and the electrons, are affected by electromagnetic power
sources such that the temperatures of the charged particles are higher than the temperature
of the atoms and therefore also higher than the original gas temperature. Note that
recombination may increase the atom temperature. However, ionisation degrees are usually
such low that this effect is small.
For plasmas in equilibrium all particles have identical temperatures by definition. In
such case it is expected that the temperature of the plasma is higher than the gas tem-
perature. In common plasmas the electrons dominate the collisions such that the electron
temperature is dominating the temperature of the plasma.
One should keep in mind that what we are discussing here is not an overall picture
anymore. For example highly ionised plasmas, recombination plasmas, and (magnetically)
enclosed plasmas are not included. At this moment we will consider them as extraordinary
plasmas.
From the discussion above one would argue that the transition from gas to plasma does
not occur at constant temperature. However, we expect that the transition to a plasma
occurs gradually. At the transition point the ionisation degree is such low that the energy
captured by the electrons and the ions can be neglected. In this case, the temperatures of
the charged particles are roughly equal to the atom temperature, which is roughly equal to
the original gas temperature. This is similar for plasmas in equilibrium. Just after the
transition the charged particles may gain energy from the power source, recombination
may increase the atom temperature, and a magnetic field may enclose the plasma.
According to this scheme, the plasma is first created (ignited) and secondly shaped

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(sustained). While the plasma is sustained new plasma can be ignited such that the plasma
is growing. Note that the extraordinary plasmas can fit in the ignition-sustaining picture.
Now one would argue again that the transition from gas to plasma (the plasma ignition)
occurs at constant temperature.
It is therefore expected that the transition from gas to plasma occurs isothermally when
the transition can occur gradually following the ignition-sustaining picture. At a more
drastic transition from gas to plasma, it is expected that the transition is non-isothermal.

Conclusion

Plasmas are not another phase which is implied by the statement that the plasma state is the
fourth state of matter in the sequence: solid, liquid, gas, and plasma. The transition from
gas to plasma differs from the other transitions, which are first-order phase transitions. The
word fourth is misleading. Plasma is not a fourth phase. One could also argue that the
comparison with the three phases is misleading. Avoiding the word phase and using
the word state in the statement about the three phases (solid, liquid, gas) and the fourth
state (plasma) is confusing.
Instead of the Gibbs free energy G, the Helmholtz free energy F seems to be a better
thermodynamic state function to describe the transition from gas to plasma. Ionisation is
mimicking the latent heat of first-order phase transitions. The transition occurs at constant
volume rather than at constant pressure.

Acknowledgments PlasmAIX for plasma physics and chemistry research is acknowledged.

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