Andrew’s experiment

CONTINUITY OF STATE
 Introduction: Andrew’s Experiment

 Gases can be liquefied by decrease of temperature or increase of pressure or by

combined effect of both.However,the effect of temperature is rather more important
than that pressure.The essential condition for liquification of gases were studied by
Thomas Andrews in1869.
 Thomas Andrews 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. Andrews observed that at high
temperatures isotherm look like that an ideal gas and gas cannot be liquified 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.
 Isotherm of Carbon
dioxide at 13.1°C
S
1. Andrews performed a experiment Of
pressure volume relationship (isotherm)of
carbon dioxide gas at series of
temperature.Consider a isotherm PQRS at
13.1°c .The point P represent carbon
dioxide in gaseous state occupying a certain
volume under a certain pressure.On
increasing the pressure,it’s volume decrease
as is indicated by the curve PQ. At Q ,which
represents a pressure of 49.8 atm.At the

Liquid
point Q liquefaction of the gas starts and
thereafter a repid decrease in volume takes
place at the same pressure.At point R gas
has been completely liquified.Now as the
liquid is only slightly compressible, further R Q
increase in pressure,there is a very small
decrease in volume.Thus along curve PQ
13.1°C Gas
carbon dioxide exist as gas,along RQ exist
partly as gas and partly as liquid,while P
along RS it exists entirely as liquid.
Isotherm of Carbon
dioxide at 21.5°C
S
D

The isotherm 21.5°C shows a

d
Liqui
similar behaviour.In this isotherm
carbon dioxide exists as gas along
AB . At the point B liquification of
gas starts and volume sharply
decrease .At the point c C 21.5°C B
Liquification is complete.Further G
increase in pressure on the as
liquid(FromC to D)brings about a
very small decrease in the volume.In
this case horizontal portion CD R 13.1°C Q
A
where both liquid and gaseous state
can co-exist becomes smaller. P
 H 31.1°C

Isotherm of carbon S D
dioxide at 31.1°C
E
At still higher temperatures,the
horizontal portion of the curve
becomes shorter and shorter untill
at 31.1°C, it reduce to just a point
Andrews concluded that if the
temperature of carbon dioxide is B
above 31.1°C,it cannot be C
liquified,no matter how high the
pressure may be.He called 31.1°C F
as the critical temperature of carbon
dioxide R Q
A
P
 50°C
H
Isotherm of carbon
dioxide above
S D
critical temperature.

.It is clear from the figure that at E

50°c (i.e.above the critical
temperature) the isotherm for
carbon dioxide is similar for ideal C B
gas..
F

R Q
A
P
 S

On joining the ends of the

horizontal portion of various
isotherm,a boundary curve is
obtained as shown in the fig. At the
top of the critical point
E( lies3.1.1°c)Within the area of the
boundary curve,both liquid and
gaseous states can co-exists but out F
side the area either liquid or
gaseous state alone can exists.
R Q
P
 Continuity of
state S
Let us suppose a certain volume of carbon dioxide, represented by X
Y
a point P on the PQRS isotherm 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(72.9 atm for carbon dioxide).Let the
gas be now cooled at the same pressure,the temperature and
volume both will decrease along XY.At Y carbon dioxide exists as
liquid.During the 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 be overcome by the van der Waal
forces of attraction.They are as close as they are ,when in the liquid
state.Thus at point y they ,all get condensed in to liquid state.The
process of transition from gaseous state to liquid state or vice-versa
,therefore is regarded as continuous
R Q
P