Andrew's Experiment

INTRODUCTION
Gases can be liquefied by lowering the temperature or increasing the

pressure .In middle of the 19 th century, a number of gases such as carbon dioxide Sulfur
dioxide Hydrogen sulfide, where liquefied by combined effect of cooling. According to
kinetic molecular model of gases, the forces of attraction between the molecule are
negligible. When the temperature of the gas is lowered, the kinetic energy of the
molecule decreases. As a result the slow moving molecule come nearer to one another .
At a sufficiently low temperature, some of the slow moving molecules cannot resist the
force of attraction and they come closer and closer and ultimately the gas changes into
the liquid state.
The essential condition for liquefaction of gases were studied by Thomas Andrews
in 1869. He studied the pressure volume temperature relation in gaseous and liquid
state of carbon dioxide .He measured the variation of volume of carbon dioxide with
pressure at various constant temperature and plotted isotherm of carbon dioxide at
different temperatures .Andrews observed that at high temperatures isotherm look like
that of an ideal gas and gases cannot be liquefied even at very high pressure .As the
temperature is lowered, the shape of the curve changes and data shows more and more
deviation from ideal behaviour .This is because carbon dioxide does not behave ideally
as the temperature becomes lower and lower.
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ANDREW’S EXPERIMENT
Fig:1 P-V isotherm of carbon dioxide.
The importance of critical temperature of a gas was first discovered by Thomas

Andrews in his experiment on P-V isotherms of carbon dioxide at series of temperatures
.The isotherms of carbon dioxide determine by him at different temperatures as shown
in the fig.:1.Let us consider the first isotherm at lowest temperature 13.1°C. The point P
represents carbon dioxide in gaseous state occupying a certain volume under a certain
pressure. On increasing the pressure the volume decrease as indicated by the curve PQ.
At Q which represents a pressure of 49.8 atm, liquefaction of gas commences and
thereafter a rapid decrease in the volume takes place at the same pressure, as more and
more of the gas is converted in to liquid state. At R, the gas has been completely
liquefied. Now, as the liquid is only slightly compressible, further increase of pressure
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produces only a very small decrease in the volume. This is shown by a steep line RS
which is almost vertical.
Thus along curve PQ, carbon dioxide exists as gas, along. QR is exists partly as
gas partly as liquid, while along RS it exists entirely as liquid. It may be noted that a
considerable decrease of volume takes place when the gas changes in to liquid state
at constant pressure.
The isotherm ABCD at 21.5°C shows a similar behaviour expect that now the
liquefaction commences at a higher pressure and horizontal portion BC,
representing decrease in volume, becomes smaller. At still higher temperatures, as
the horizontal portion of the curve becomes shorter and shorter until at 31.1°C it
reduces to just a point. At this temperature therefore gas passed into liquid state
imperceptibly. Above 31.1°C the isotherm is continuous. There is no evidence of
liquefaction at all. Andrew concluded that if the temperature of the carbon dioxide
is above 31.1°C,it cannot be liquefied , no matter how high the pressure may be.
Below 31.1°C each curve shows the similar trend expect that the length of the
horizontal line increases at lower temperature. All the gases under compression at
constant temperature (isothermal compression) show the behaviour similar to the
behaviour of carbon dioxide. Thus, we observe that at 31.1°C the isotherm has a
very small flat portion virtually reduced to a point E. Above 31.1°C there is no flat
portion indicating that under all pressure, it remains in gaseous state. Generally,the
gases below their critical temperatures are called vapour.
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CRITICAL CONSTANT
Andrew concluded that there is a certain temperature above which a gas cannot
be liquefied no matter how pressure may be applied. The gas can be liquefied only
below this temperature. This characteristics temperature is called critical temperature.
Thus critical temperature is the temperature above which a gas cannot be liquefied
however high pressure may be.
Since then, other gases have been found to behave similarly. There’s no
fundamental difference between the so called permanent gases such as hydrogen,
oxygen nitrogen etc. and temporary Such as carbon dioxide, chlorine, ammonia etc. The
difference lies in the fact that while the so called permanent gas have very low critical
temperature must below the ordinary range of temperature and so called temporary
gases have critical temperature well within the range of ordinary temperature.
At critical temperature of the liquid and gas phases of a substance enclosed in
vessel merge into one another and there is no boundary. i.e. meniscus between the two
phases disappears. i.e. there is only one continuous dense phase called supercritical
fluid. Thus a substance at and just above its critical temperature and pressure is called
supercritical fluid.
Thus we observed that at 31.1°C,there is no flat portion indicating that under all
pressure it remains in gaseous state. Generally the gases below their critical
temperature is called vapour. In terms of critical temperature, a gas can be liquefied
below the critical temperature by applying pressure. Therefore above the critical
temperature it is vapour.
Increase of pressure has also the effect of bringing the gaseous molecule closer and
closer to one another. Thus, the minimum pressure needed to be applied at critical
temperature, so that the given liquid is liquefied is called critical pressure. Volume
occupied by one mole of a gas at its critical temperature and critical pressure is called
critical volume.
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CONTINUITY OF STATE
Fig:2 P-V isotherm of carbon dioxide(continuity of state)
A careful examination of isotherm plotted in fig:2. Shows that it is possible to

convert liquid carbon dioxide into gas and vice-versa without having any discontinuity.
i.e. without having more than one phase at any time. On joining the ends point of the
horizontal portion of the various isotherm a boundary curve, represented by dotted line
is obtained. At the top lies the critical point E(31.1°C).Within the area of the boundary
curve, both liquid and gaseous states can co-exist but outside the area, either liquid or
gaseous state alone can exist
Suppose a certain volume of carbon dioxide, represented by a point P on the 13.1°C
isotherm PQRS is heated at constant volume to a temperature at which the pressure
increase to a point x, lying above the critical pressure of the gas. Let the gas be now
cooled at the same pressure ,the temperature and volume decrease along xy. At y
carbon dioxide exists as liquid. During this transition from gas to liquid, there has never
been more than one phase present at any time. As the temperature is decreased from x
to y, the volume of the gas decrease gradually till the molecule are close enough to
overcome by van der Waal forces of attraction. They are as close as they are, when in
the liquid state. Thus at point y, all get condensed into liquid state. The process of
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transition from gaseous state to liquid state, or vice versa therefore is regarded as
continuous.
CONCLUSION
The process of change from gaseous state to liquid state, therefore is

regarded as continuous. Thus there is a continuity between the gaseous and liquid state.
To recognise this continuity, the term fluid is used for either a liquid or gas. A liquid can
be viewed as a very dense gas. The liquid and gas can be distinguished only when the
fluid is below the critical temperature. In this situation, the liquid and the gases are in
equilibrium.
At critical temperature, liquid changes into gaseous state imperceptibly and
continuously and the surface separating these two phases disappears. A gas below it’s
critical temperature can be liquefied by applying pressure and is called vapour of the
substance. Carbon dioxide below it’s critical temperature is called carbon dioxide
vapour.
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INTRODUCTION

Gases can be liquefied by lowering the temperature or increasing the

Fig:1 P-V isotherm of carbon dioxide.

The importance of critical temperature of a gas was first discovered by Thomas

Fig:2 P-V isotherm of carbon dioxide(continuity of state)

A careful examination of isotherm plotted in fig:2. Shows that it is possible to

The process of change from gaseous state to liquid state, therefore is

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