2.3 Steady state vs.

Equilibrium 17

2.3 Steady state vs. Equilibrium

Let us start with a common example a metal rod in contact with boiling water at one
end and dipped in melting ice at the other end as shown in figure 2.3. We are con-
cerned with only the properties of the metal rod, for the time being, and define this
as our system. Initially, lets say the rod was at room temperature (300C) and at the
instant it is brought in contact with the hot (1000C) and cold (00C) bodies, the two
ends attain the respective temperatures. With progressing time, heat diffuses along
the rod and more and more of the rod length is affected by the end temperatures. This
continues until the rod attains a uniform temperature gradient (for uniform conduc-
tivity material along the rod), i.e. temperature varying linearly from one end to the
other. After the initial development (often called the transient period), the tempera-
ture profile along the rod is fixed. T = f (x), but at any point, T does not change with
time. This is called the steady state, where heat is continuously transferred from the
hot to the cold end, but the properties of the system are independent of time.

Boiling water Melting ice

0
100 C 00 C
Metal rod

1000 C
time

00 C
X

Fig. 2.3 T vs x to steady state

Now, take the rod out of contact with the hot and cold bodies, and isolate it, i.e.
allow no energy/heat transfer from or to it. The mass of our system is fixed, and
the energy contained remains unchanged. This is called an isolated system, with
no energy or mass transfer across its boundaries. For the isolated rod, there will
be transfer of heat from the hot to the cold end. The hot end becomes cooler and
the cold end progressively gets hotter, and after a long time, the whole rod attains
a uniform temperature, and no further changes are observed. The system is now
in equilibrium. Figure 2.4 show the system in equilibrium state. A system is in a
state of equilibrium, when its properties are uniform and only one value through
18 2 Basic Concepts

out, and no spontaneous change is possible as long as the system is isolated from
its surroundings. For a system in equilibrium, the macroscopic properties do not
change, but microscopic activities do not stop.

1000 C

T
t

00 C

Fig. 2.4 T vs x to equilibrium

There are different types of equilibrium – thermal equilibrium, mechanical equilib-

rium and chemical equilibrium shown in figure 2.3. Thermal equilibrium is achieved
when we have uniform temperature throughout the system, as in the example able.
Mechanical equilibrium is associated with uniform pressure, as long as we neglect
gravity effects (as we often do in aerospace engineering). Chemical equilibrium is
characterized by uniform composition of the gas in the entire system.

Two bodies at different temperatures are brought in diathermal contact (that allows
the flow of heat) using a metal rod, for example. The combined system is in thermal
non-equilibrium, as there will be energy exchange between the hot and cold parts,
due to the temperature gradient across the connecting rod, until the two bodies attain
identical temperatures.

An analogous scenario can be imagined where two containers with gases A and B
are connected through a pipe. The gases diffuse from one side to the other, due to the
concentration gradient, until after a long time, we are left with a uniform mixture of
the two gases throughout the system. Composition of a gas can also change due to
chemical reactions, and we have to wait for the completion of the reaction to achieve
chemical equilibrium. Chemical reactions are generally associated with heat release;
a chemical non-equilibrium can therefore result in thermal non-equilibrium as well.

Finally, mechanical non-equilibrium is caused by a difference in pressure between

different parts of a system, as in the case of a compressed vessel connected to an
evacuated one. The pressure difference leads to flow velocity through the connecting
pipe, so as to equalize the pressure between the two vessels.
2.3 Steady state vs. Equilibrium 19

A system in thermal, chemical and mechanical equilibrium is then in thermody-

namic equilibrium. Thermodynamic properties of a system are defined only when
the system is in a thermodynamic equilibrium state. Otherwise, there would not be a
unique value of temperature, pressure or chemical composition for the system. The
values also should be independent of time, as in thermodynamics, we mainly study
the equilibrium states of a system.

TA TB

[a]

A B

[b]

PA PB

PA > PB
[c]

Fig. 2.3 Systems in different types of non-equilibrium. (a) Thermal, (b) chemical, and (c) Me-
chanical equilibrium