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Lecture 2b

Lecture 2b: Independent Properties of Pure

Substance
Independent properties
Let us define a

 SIMPLE COMPRESSIBLE SUBSTANCE: a material that can be worked upon by

pressure forces.

Note we neglect electric, magnetic, and chemical work modes. While this is indeed
restrictive, it will be important for many mechanical engineering applications. The following
important statement can be proved (but will not be so here):

 For a simple compressible substance, two independent intensive thermodynamic

properties define the state of the system.

Consider the implications for

 SUPERHEATED VAPOR: If we consider 𝑃 , 𝑇 , and 𝑣, this states that we must allow

one of the variables to be functions of the other two. We could have 𝑃 = 𝑃 (𝑇, 𝑣),
𝑣 = 𝑣(𝑇, 𝑃 ), 𝑜𝑟 𝑇 = 𝑇 (𝑃, 𝑣). All are acceptable.
 TWO-PHASE MIXTURE: If we have a two-phase mixture, our experiments show
that 𝑃 and 𝑇 are not independent. In this case, we need another property to
characterize the system. That property is the quality, 𝑥. So for two-phase mixtures, we
might have 𝑣 = 𝑣(𝑇, 𝑥), for example.

Thermal equations of state

Here, we will describe some of the many different ways to capture the relation between two
independent properties and a third dependent property for a simple compressible substance.
We will focus on a so-called

THERMAL EQUATION OF STATE: an equation which gives the pressure as a function of

two independent state variables. An example is the general form:

𝑃 = 𝑃 (𝑇, 𝑣)

We will progress from simple thermal equations of state to more complex.

Ideal gas law

For many gases, especially at low density and far from the critical point, it is possible to write
a simple thermal equation of state which accurately describes the relation between pressure,
volume, and temperature. Such equations were developed in the 1600s and early 1800s based
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Lecture 2b

entirely on macroscopic empirical observation. In the late 1800s, statistical mechanics

provided a stronger theoretical foundation for them, but we will not consider that here.

Let us start with the most important equation of state:

 IDEAL GAS LAW: This equation, which is a combination of Boyle’s law, Charles’
law, and Avogadro’s law, is most fundamentally stated as

𝑃 𝑉 = 𝑛𝑅𝑇

The data in (𝑉, 1/𝑃 ) space is fit well by a straight line with intercept at the origin; that is
1/𝑃 = 𝐾𝑉, where K is a constant. Thus, 𝑃 𝑉 = 𝐶, where 𝐶 = 1/𝐾 is a constant.

Figure 2.1: plot of Boyle’s data: V versus reciprocal of P, demonstrating its near linearity.

The ideal gas law was first stated in the form roughly equivalent to above equation by
Clapeyron.

It is critical that the temperature here be the absolute temperature. Here, n is the number of
moles. Recall there are 𝑁 = 6.02214179 × 1023 molecules in a mole, where 𝑁 is
Avogadro’s number. Also R is the universal gas constant.

From experiment, it is determined to be

𝑅̅ = 8.314472 𝑘𝐽/𝑘𝑚𝑜𝑙𝑒 𝐾

In this class the over bar notation will denote an intensive property on a per mole basis.
Intensive properties without over bars will be on a per mass basis. Recall the mass-basis
specific volume is 𝑣 = 𝑉/𝑚. Let us define the mole-based specific volume as

𝑣̅ = 𝑉/𝑛

Thus, the ideal gas law can be represented in terms of intensive properties as

𝑉
𝑃 = 𝑅̅ 𝑇,
⏟
𝑛
=𝑣̅
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Lecture 2b

𝑃𝑣̅ = 𝑅̅ 𝑇.

There are other ways to write the ideal gas law. Recall the molecular mass M is the mass in g
of a mole of substance. More common in engineering, it is the mass in kg of a kmole of
substance. These numbers are the same! From chemistry, for example, we know the
molecular mass of 𝑂2 is 32 𝑔/𝑚𝑜𝑙𝑒 = 32 𝑘𝑔/𝑘𝑚𝑜𝑙𝑒. Symbolically, we can say that

𝑚
𝑀 =
𝑛

Now, take the ideal gas law and divide by m:

𝑃𝑉 = 𝑛𝑅̅ 𝑇,

𝑉 𝑛
𝑃 = 𝑅̅ 𝑇,
⏟
𝑚 ⏟
𝑚
=𝑣 =1/𝑀

𝑅̅
𝑃𝑣 = 𝑛 𝑇,
𝑀

Now, let us define

𝑅 ≡ 𝑅̅ / 𝑀.

Let’s check the units:

𝑘𝐽 𝑘𝑚𝑜𝑙𝑒 𝑘𝐽
[𝑅] = =
𝑘𝑚𝑜𝑙𝑒 𝐾 𝑘𝑔 𝑘𝑔 𝐾

We have actually just lost some universality. Recall R is independent of material. But since
each different gas has a different M , then each gas will have its own R. These values for
various gases are tabulated in Table A.5 of BS.

With this definition, the ideal gas law becomes

𝑃 𝑣 = 𝑅𝑇.

This is the form we will use most often in this class. Note the useful fact that

𝑃𝑣
= 𝑅.
𝑇

Thus, if an ideal gas undergoes a process going from state 1 to state 2, we can safely say

𝑃1 𝑣1 𝑃2 𝑣2
=
𝑇1 𝑇2