Lecture 2

Perfect Gas & Zeroth Law of

Thermodynamics

2.1 Thermodynamics

Thermodynamics deals with relationships among the macroscopic properties of matter.

These relationships are derived from the laws of thermodynamics. The laws are derived
from a wide variety of observations and ultimately justified by the agreement of the
conclusions drawn from them with experiments.
Thermodynamic relationships are true only for macroscopic systems in equilibrium.
They can be extended to non-equilibrium conditions. They are related to microscopic
particles of the system, e.g., the interaction between molecules, particle velocities, etc.
Some basic definitions:

• System: a part of the physical world under consideration.

• Surroundings: part of the physical world that is not part of the system

• Closed System: does not exchange matter, may still be able to exchange energy
with surroundings.

• Isolated System: has no interactions with the surroundings.

Thermodynamic state of a system is assumed to be determined by a complete set

of independent macroscopic coordinates or variables. Given the mass of the system,

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these coordinates are just those variables that must be independently specified for one
to reproduce a given thermodynamic state, as determined by experiment.
Usually, the number of independent variables required to define the thermodynamic
state is very small. For a gas or a liquid (i.e., a fluid), the shape has no importance
in determining the properties. For a pure fluid, i.e., containing only one chemical
species, in the absence of external fields, pressure and volume uniquely defines the
thermodynamic state. A unique relationship among pressure, volume, and any other
thermodynamic variable X can be expressed as

f ( P, V, X ) = 0 . (2.1)

The above is called equation of state.

Thermodynamic variables can be either intensive or extensive. Intensive variables
are independent of the size of the system, while extensive variables depend on the
size of the system. The ratio of two extensive variables will be an intensive variable.
Examples of intensive variables are pressure, density, and temperature. Examples of
extensive variables are volume, mass, internal energy, and entropy.

2.2 Temperature and Zeroth Law of Thermodynamics

Consider a situation where the two systems are separated by a rigid barrier B. If barrier
B is an adiabatic wall, i.e., particles and energy transfer are not permitted, then the two
systems remain unchanged from the initial states. Thus, the temperature of the two sys-
tems remains different. Consider another situation where the barrier B is diathermal,
i.e., allows the heat flow. In such a case, heat flow happens from the hot system to the
cold system until they approach thermal equilibrium. When the system reaches equi-
librium, then one cannot change the state of system 1 without simultaneously changing
the state of system 2.
The zeroth-law of thermodynamics was introduced by H. von Hemlholtz in 1884.
The law states: Two systems, each separately in thermal equilibrium with the third system,
are in thermal equilibrium with each other. E.g., if systems 1 and 2 are at the same tem-
perature and are separately in equilibrium with a mercury-in-glass thermometer, the

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temperature of the system will be the same if we bring systems 1 and 2 into contact.
In thermal equilibrium, the temperature of the two systems in contact will be the
same. If the temperature of the two systems were not initially the same, and if they
were brought to contact, then the temperatures of both systems would change and
becomes equal.
The zeroth-law is important for the definition of temperature scale.

2.2.1 Ideal Gas Temperature Scale

PV
T = lim (2.2)
P →0 R

where V = V/n is called the ideal gas temperature. The unit of thermodynamic tem-
perature, 1 Kelvin (K), is defined as the fraction 1/273.16 of the temperature of the
triple point of water. In other words, the triple point of water is defined at 273.16 K.
The temperature 0 K is called absolute zero. The freezing point of water is at 273.15 K,
and the boiling point is 373.12 K at 1 atm.

t◦ /C = T/K − 273.15

In the Celcius scale, the temperature scale is defined in terms of two fixed points,
namely the temperature of melting of ice and boiling of water at 1 atm pressure. Celsius
scale of temperature is obtained by setting the boiling point of water as 100◦ C, melting
ice as 0◦ , and dividing the interval by 100 degrees. In the following figure, V is plotted
versus the Celsius temperature t at different pressures for a dilute gas. Experimentally,

P1
P2
V

P2 > P1

−273.15 0 t/∘ C

Figure 2.1: V versus temperature given by Gay-Lussac’s Law for two different pressure for a
dilute gas.

molar volume extrapolates to zero for all the gases at all pressures at −273.15◦ C. We

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will see later that the ideal gas temperature scale is identical to the one based on the
second law of thermodynamics.

2.3 Definitions to Remember

• One mole of a ubstance has as many atoms or molecules as 12 g of 12 C.

• Molar mass M = mass of the substance divided by the number of moles of the
substance (kg mol−1 ). Also, M = NA m, where m is the mass of the single molecule
(molecular mass), and Avogadro constant NA = 6.022 × 1023 mol−1 .

• Gas constant R = 8.314 J K−1 mol−1 = 0.083 L bar K−1 mol−1 = 0.082 L atm K−1 mol−1

• kB NA = R

• 1 atm = 101 325 Pa = 1.013 bar.

• 1 cal = 4.184 J

2.4 Ideal Gas Mixtures and Dalton’s Law

For a mixture of ideal gases,

P = (n1 + n2 + · · · ) RT/V (2.3)

= n1 RT/V + n2 RTV + · · · (2.4)

= P1 + P2 + · · · = ∑ Pi (2.5)
i

This is Dalton’s Law. Here, Pi = ni RT/V. If n = n1 + n2 · · · , then

Pi = ni P/n = yi P (2.6)

Here, yi is the mole fraction of the ith gas. Clearly, ∑i yi = 1.

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 P = P1 + P2

P1 = y1P

Pressure
P2 = y2P

0 y2 1

Figure 2.2: Variation of partial pressures P1 and P2 , as well as total pressure P with respect to
mole fraction y2 ≡ 1 − y1 for a binary ideal gas.

2.5 Real Gases and The Virial Equation

At the limit of low pressures and high temperatures, a real gas can behave like ideal
gas. To quantify the deviation from ideality, we use compressibility factor

PV
Z= .
RT

Any deviation from Z = 1 indicates deviation from ideality. See Figure 2.3; at low
pressures, Z is close to 1.0. One can also see that real gases can have Z > 1 as well as
Z < 1 depending on the pressure. At very high pressures, real gases show Z > 1. This
can be explained based on the finite size of the gas molecules. At very high pressures,
the molecules of the gas are pushed closer together and the volume of the gas is larger
than expected from the ideal gas because a significant fraction of the volume is occupied
by the molecules themselves.
At low pressures, a gas can have Z < 1. This can be explained based on the in-
termolecular interactions. At the limit of P → 0, the distance between the molecules
should go to infinity. At the limiting values, this condition is not becoming fulfilled
when there are interactions between the gas molecules. In Figure 2.4 it is clear that for
Z deviation from ideality varies with temperature. When temperature is lowered, the
inter molecular attraction increases, and thus molar volume is smaller than in ideal gas.
All gases show a minimum in Z − P plot at sufficiently low temperatures.
Modified equations of states were proposed to account for the real gas behaviors.

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 N2
2.0 O2

Z 1.0

200 400 600

P/bar

Figure 2.3: Variation of Z with pressure for two real gases at 298 K

2.0 N2 298K
573K

Z 1.0
273K

200 400 600

P/bar

Figure 2.4: Variation of Z with pressure for N2 real gas at various temperatures

One such example is the virial equations of state:

PV B C
Z= = 1+ + 2 +··· (2.7)
RT V V
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Here a power series in V
is used. B and C are constants for a gas, and are called
second and third virial coefficients. For a particular gas, these coefficients depend on
the temperature, but not on pressure.
In many cases, it is preferred to use virial equations of state as a function of P,
instead of V:

PV
Z= = 1 + B ′ P + C ′ P2 + · · · (2.8)
RT