Continuity of States

In the figure, A and D lie on the same isotherm at 13.1 oC temp., Two-phase region and continuity of states
below the Tc of CO2.
Cooling at
Cooling at const. Pr.
Point A → gaseous state
const. Vol
Point D → liquid state
Dashed area → contains liquid-gas in equilibrium Heating at
const. Vol
It is possible to shift from the gaseous state point A to the liquid
state point D continuously without passing through the
discontinuous dashed area.

✓ Let the gas at the state point A is heated to B at constant vol. along AB.

✓ Then, the gas is gradually cooled at constant pressure along BC, the vol. is reduced considerably.

✓ The gas is again cooled at constant vol. until the state point D is reached.

✓ No where in the process liquid would appear. At D, the system is highly compressed gas. But the
curve shows that this state point is for the liquid state.

✓ Thus, there is hardly any difference between the liquid state and the gaseous state and there is no
line of demarcation between the two phases. This is the continuity of states.

✓ The point D we may refer as liquid state or highly compressed gaseous state. In the absence of
discontinuity there is no fundamental way to distinguish liquid or gas.

✓ The gas is continuously transferred to the liquid without passing the usual process of condensation.
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 Continuity of States

✓ At the critical temperature, the boundary between the liquid phase and gas phase disappears.

✓ The densities of the substance in the two phases are the same.

✓ Continuity of state is the property of a transition between two states of matter, as between gas
and liquid, during which there are no abrupt changes in physical properties.

✓ Thus, the transformation from the gaseous state to the liquid state or vice versa may be made
gradually, without passing through the phenomenon of condensation.

✓ Nowhere during the transformation two phases will co-exist.

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Continuity of States

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 Andrews isotherm for 1 mole CO2
What is the physical significance of the volume range being
widened with decreasing pressure??

Answer: You are changing temp.

Physical significance: You need higher saturation Pr., so the range
of vol. over which condensation occurs is smaller.

How can liquid and gaseous states be the same?

Answer:
Two-phase region and continuity of states
They are not same. There is no line of demarcation between
the two phases. This is the continuity of states.

In the absence of discontinuity there is no fundamental way to

distinguish liquid or gas. The gas is continuously transferred to
the liquid without passing the usual process of condensation.

Question
Inside Jupiter, liquid hydrogen is found. But the temperature of Jupiter is extremely high and
definitely above the critical temperature of hydrogen. So how is liquid hydrogen found in Jupiter?
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 Critical Phenomena and Vander Waals Equation
VDW Isotherm for 1 mole CO2

Taking the values of a and b for CO2, it is possible to collect

data P and V at 13.1, 21.1, 31.1 and 50 oC, and draw the similar
isotherms like that of Andrews.
→ Vander Waals isotherms

The experimental Andrews isotherms coincide with the Vander

Waals isotherms in all the points except the region where the
gas and liquid are co-existing.

The horizontal lines are replaced by wavy lines. These wavy

portion of Vander Waals curves poses two limitations of the Tc = 31.1 oC; Pc = 72.9 atm and Vc = 94.2 cc/mol
VDWE which are not realized in practice.

The isotherm pqrst shows that there are three volumes of the system at a give T and P.

Again at the portion srq, it shows that with increase of Pr., vol. is also increased.

These two points show the limitations of VDWE.

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Relation between critical constants (Pc, Vc and Tc) and Vander Walls constants (a and b)

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 Relation between critical constants (Pc, Vc and Tc) and Vander Walls constants (a and b)

Thus, critical coefficient is predicted

constant for all VDW gases.

Thus, at the critical state, the gas is

more compressible.

These values are tested experimentally whether the critical coefficient is constant and = 2.66
for all gases but it is found that it varies from gas to gas and the average value is about 3.66.

Applications: Calculations of Vander Waals constant a and b.

The critical constants of a gas can be

determined experimentally and so the values of
the VDW constants a and b can be calculated.
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 Reduced form of Vander Waals Equation of State
VDWE can be expressed in terms of their reduced variables in stead of T, P and V. The reduced
variables are defined as the actual variables divided by the corresponding critical constants. Thus,

Replacing P, V and T in the VDWE by corresponding reduced variables, we have

✓ The important feature of the equation is that it is independent of VDW constants, a and b.
✓ Thus, it appears that the equation is independent of the nature of the gas and general as it is in ideal
gas equation.
✓ But it is not true. The characteristic gas constants now remain disguise within the reduced variables
(,  and ) as these variables contain critical constants (Pc, Vc and Tc) and these are characteristic
constants of the gas.
✓ Thus, it is not that generality lost in VDWE is regained in this form.
✓ The reduced equation of state gives birth one important generalization, called law of corresponding
states. 8
 Limitations of Vander Waals Equation

So, we can conclude that VDWE explains the behaviour of the real gas qualitatively but it fails to explain
quantitatively.

The equation of state of a gas can be satisfactorily expressed as a power series of Vol. or Pr., suggested
by H. Kammerlingh-Onnes in 1901 as;

Nobel Prize in Physics (1913)

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 Kammerlingh-Onnes Virial Equation

✓ TB → The temperature at which real gases obey ideal gas equation over an appreciable Pr. range

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Real Gases: Explanation of Amagat’s Curves in the Light of VDW Eq.

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 Questions
Along the critical temp. isotherm, the slope is zero at the critical point (C) and is –ve on either side of the
point. Thus, the slope is maximum (zero value is greater than –ve values) at the critical point. This slope
is function of V and its derivative w.r.t. V is again zero at the point.

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