EQUATION OF STATE 63

the year 1847. Increasing the

results were obtained by Regnault in
and
3 pressure range up to 30 atmospheres to
Hz,He

0°C
Varying temperature between
100°C, he drew (PV - P) isothermals PV
EQUATION OF STATE found that the
for different gases and Perfect gas
isothermals were not parallel to pressure
3.1. Equation of state; deviation from the perfect gas equation axis but were inclined. For allreal gases,
The equation formed by some selected variables for a substance like O, N, and CO, the product PV O2, N2,cO
which represent the behaviour of the substance is generally called the decreases with pressure while for gases
equation of state of the substance. Usually pressure (P), volume (V) like H, and He, PV- values increase (Fig.
and temperature (T) are selected as variables for a substance. 3.1) but none gave a straight line curve. Fig. 3.1
Thus combining Boyle's and Charle's laws, we get for a perfect gas The former class of gases are called less
PV = RT. This equation connecting P,Vand T may be called the perfect and the latter class, more perfect.
carried out elaborate
equation of state ofa perfect gas. The equation contains one constant Later on Andrews, Cailletet and others
pressures and found
viz the gas constant R. Depending upon the values of any two investigations on the behaviour of real gases at high
equation. It was,
variables, the third variable will have a particular value which can be that almost all gases deviated from the ideal gas permanent
found out from the equation. But in reality this does not always happen. therefore, established beyond all doubts that the so-called
Andrews are of special
Boyle's and Charles' laws, i.e, the equation of state mentioned above, gases are not perfect gases. The experiments of regarding
are obeyed strictly by an ideal or a perfect gas at all temperatures significance because they provided valuable information
to the
and pressures. So, if a curve be drawn between the volume ( V) and liquefaction of gases by the application of pressure and led Waals
new equation of state known as Van der
pressure (P) at a constant temperature for a given mass of a perfect establishment of a
are dealt
gas, the curve, according to the equation of state, should be arectangular equation of state. This experiment and its associated results
hyperbola. Alternatively if a curve is drawn between PV plotted along with in a subsequent article.
the vertical axis and P along the horizontal axis at a constant Perhaps the most significant experiment regarding the behaviour of
temperature the curve will be a straight line parallel to the pressure gases towards Boyle's law was done by Amagat in 1880. Applying
axis bccause PV is a constant. These curves are known as apressureas high as 3000 atmosphere on nitrogen, hydrogen and carbon
isothermals for the gas. If, for any real gas, the isothermals are found dioxide he cbtained from their isothermals, some useful and important
to be other than staight lines, it willindicatethat the gas does not strictly data regarding the behaviour of the so--called permanent gases. This
obey the gas law. How much does the behaviour of a real gas deviate experiment also will be discussed in a subsequent article.
from that of a perfect gas can also be estimated from the difference In the later years, K. Onnes investigated the behaviour of gases at
betwecn the isothermals of a real gas and the straight line isothermal very low temperature and found that the variations of the PV values
of a perfect gas. with the change of pressure (P) at any temperature is very well
Boyle himself found from his experiments that all gases, in general, represented by the following empirical equation:
behaved according to his law only at high temperatures and low
PV = A + BP + CP' + DP + (i)
pressurcs (from 0.03 atmosphere to about 4 atmosphercs ). In 1827
Despretz extended the pressure range to 20 atmospheres on equal Here, A, B, C, etc. are constants depending on temperature. They
volumes of different gases and came to the conclusion that some gases are called virial coefficients. A is the first virial coefficient, B, the
did not obey Boyle's law exactly. But, perhaps, the first trustworthy second and so on. Clearly A= RT because when the pressure (P)

62
 DEGREE PIYSICS
64 A HAND BOOK OF EQUATION OF STATE 65
is very small, the above cquation should reduce to the ideal cquation
know PV = constant or,
Vz PV RT. At Boyle temperature, we dP
But from cqn. (i) we get
PV = A + BP + Cp' + ...
3.2. Boyle temperature (Tp) when Pis very small.
From the results of the experimcnts carricd out by Rcgnault, Amapat . .d( P )= B+2CP + 3PD + = B,
and others on d1fferent gases, we come to know that in general, the
PV values of a given mass of rcal gas at a given temperature depend So, at Boyle temperature, B=0. is, howcver, samne for all gases.
on the pressure P But at the same time, a particular temperature is The change of this virial cocfficicnt
gradually incrcases with the
always available for cach real gas when PV values of the gas become At low temperatures, it is ncgative; it temperaturc. Finally
independent of its pressure. At that temperature, thercfore, PV - incrcase of temperature and becomes zero at Boyle
rise of tcmpcrature.
P isothermal of the gas will be parallel to pressure axis. This mcans it becomnes positive with thc further
that at that particular temperature, the real gas strictly obeys Boyle's 3.3. Amagat's experiment:
investigate
lawor the real gas behaves like a perfect gas. In fig. 3.2, the straight In 1880, Amagat performcd a serics of experiments to under high
line AB represents such an isothermal. This particular temperature how far ordinay gases deviatcd from Boyle's law specially
feature of his
is called Boyle temperature. Above Boyle temperature, PV gradually pressures and obtained very useful results. The special
increases with the increase of experiment was to set up a very high pressure with the help of a vertical
TEMP
AvOVEBOYLETEM pressure P.Consequently, for all such mercury column and the measurement of the pressure by the height
temperatures, the isothermals of real of the column. By this arrangement he was able to producea pressure
gases willbe, in ge Ilike the curve to the extent of about 3000 atmospheres.
CD. On the other, below Boylc He uscda stecl tube 300metre high, filled with mercury as manometer
AT BOYLE TEMP
temperature, P at first diminishes (M) [Fig 3.3]. The tube was
A SELOW
80YLE
TEMP_A with the increase of pressure, connccted to the vertical
E
becomes a minimum and then shaft of a coal mine and was
increases as the pressure increases. in communication with a
For this reason, the isothermals of real mercury reservoir (V) kept
gases, at temperatures below Boyle at the bottom of the mine.
M
temperature will, in general, assume Another accurately
Fig. 3.2 a shape like the curve EF. For calibrated vertical tube
example, the Bolye temperature of hydrogen is much below 0°C. So, T closed at the top and
the room temperature may be supposed to be much higher than the containing the gas under
Boyle temperature of hydrogen. Hydrogen isothermals drawn at room examination, was also in
temperature will, therefore, look like the curve CD. For other ordinary communication with the
gases, the Boyle temperature is higher than the room temperature. So, mercury reservoir. A large
Fig. 3.3
their isothermals at room temperature will take up a shape like the screw-plunger S, working in
curve EE the mercury reservoir, could produce a very high pressure. The gas
Now, the second virial coefficient B in the equation (i) in the tube T was surrounded by a water jacket A, with the help of which,
preceding article is very important because the temperature at which the temperature of the gas in the tube T couid be maintained at any
B =0is the Boyle temperature. I may be shown in the following way: desired value. The volume of the gas was read directly on the calibrated
tube and its pressure was calculated from the height of the mercury
 EQUATION OF STATE 67
PIYSICs
HAND BOOK OF DEGREE
A
66 with the incrcase
valucs, Amagat determined then increases fairly rapidly
column in the steel tube M From thcse a certain pressure and pressures.
at different exhibit a little 'sag' at low
d1fferent gases temperatures, of pressure. The curves
the (PV - P)isothermals of pressure and volume) along the vertica
plotting PV (the product of
ontal axis. The isothermale
axis and the pressure P along the horiznitrogen and carbon dioxide
actually obtaincd by him for hydrogen, respectively. Analysing the 42!
are shown in figures 3.4, 3.5 and 3.6 represents the behaviour 1Ó01
isothernals we find that cach one of them 38
of a particular class of gascs.
() The isothermals of hydrogen and hy drogcn -like thatgases as shown 34
504
3.4, at d1fferent constant temperatures, indicate the product
in fig 301
PV incrcases gradually with pressure and the isothermals are almost
parallcl, becoming rectilinear above 80 atmospheric pressure. The
30

isothernals also show that the gases (hydrogen, heliun ctc.) are less
compressible than are warranted by Boyle's law and this property 26
40 80 120 160 200 240 280 320
>P
Fig. 3.5
shown
(ii) The isothermals of carbon dioxide and the like gases as
'sag' but their general appearance is
42
in fig 3.6, exhibit pronounced
PV
1-90
38
6o'4
60
1-70
40'4 198
34
1-50
-177 PY
1-30

1-10

40 80 120 160 200 240 280 320 0-90

0-70
Fig. 3.4 0-50
of being less compressible continues up to about - 80°C in the lower
temperature region. Further, the isothermals do not exhibit any 'sag' oo 100 20O0 300 400 500 600 700 800
anywhere, thereby indicating that the isothermals or the products
PVdo not have any minimum vaule. Fig. 3.6
(iü)The isothermals of nitrogen and nitrogen-like gases as shown more or less similar to that of the isothermal for nitrogen. The product
in fig 3.5 indicate that at low temperature, the product PV first PVat first diminishes sharply with the increase of pressure, attains
decrcases with the increase of pressure, attains a minimum value at
 PHYSICS
68 A 1AND BOOK OF DIGREE EQUATION OF STATE 69

a minimum value and increases sharply thercatter with the increhse the capillary portion of the tube. Then the tube is fixed securely inside
of pressure. The minima of the cuves, however, fall upon a smooth a wide cylinder (C) such that the
curve., shown by dotted lines in fig 3.6. capillary portion may projcct out of CARBON -AIR
It will be noted that the isothermals in all the threc cases tend to
DIOXIDE
the cylinder. A screw plunger (S) is
become aimost straight and parallcl and hence similar at higher fitted at the cylinder which is filled up |M M
pressures Later expenments revcalcd that at a very low temperature by water. By working the screw
(ncarly 175 C), Isothermals of hydrogen also exh1bit an initial 'sap" plunger, pressure may be applied on
indcating that the product PV for hydrogen also attains a minimum the gas. In this way, the gas may be
valuc at lower pressurc. Hydrogen, therefore, behaves like allother subjccted to a pressure of about 400
gases spccially at low temperature. atmospheres.
We, thercfore, draw the following conclusions from Amagat's To mcasure this pressure, another D
expenmcnt: exacly similar tube A' is mounted by
(i) Ao real guses stricly obeyBoyle 's law at higher pressure. the side of the tube A. The mercury
(u) The deviation from Boyle's law is more pronounced in the case pellet Min this tube confines some
of easily liquefiable gases like carbon dioxide than the so called air (air is considercd as a permanent
permanent gases like nitrogen. gas) in its capillary portion. The tube S S
() The deviation from Boyle's law follows pracically the same A' is also fixed in a similar cylinder
(C) filled-with water and having a Fig. 3.7
auern in the case of all gases, depending upon the particular
temperature at which the obserutions are nade. screw-plunger S at its bottom. The two cylinders C and C are
connected by a narrOW Side tube D. When the screw plunger S or S
3.4. Andrews' experiment
is worked, pressure willbe exerted equally on the gases in A and A'.
It has been found from experiment that the deviation of a real gas From the volume of air
Irom Boyle's law becomes more and more pronounced, asit approaches encloscd in the tube A', its
the state of iqucfaction. Hence it is suggested that the amount of pressure can be found out
deviation of a realgas from Boyle's law has some intimate connection 100 because air is supposed to

481C 13c
D
with the liqucfaction of the gas. Andrews made elaborate investigations D obey Boyle's law strictly.
with the isothermals of carbon dioxide at different temperatures to
90} A water bath (not shown in
study the conditions of liquefaction of a gas. Valuable informmation were H the figure) surrounds the
collecied from his experiment about the general behaviour of real 80
capillary tube containing
gases-specially about the iquefaction of gases. 35
32" carbon dioxide, whose
The apparatus uscd by him is shown in fg. 3.7. Itconsists of a glass
tube A, initallyopen at both ends, its upper portion being thick-walled
capillary tube, mid portion a bit wide and the lower portion again
31 °c
C' 21'5C B'
DIOXIDE
CARBON temperature may be kept
constant at different values
by controlling the heating of
narrow. The capillary portionof the tube is carefully graduated in cm'. the bath. A similar water bath
Through the tube A, a stream of carbon-dioxide is passcd for a long 50
131C B
also surrounds the other
time and then the two ends arc propcrly scaled. The lower end is then
VOLUME
capillary tube which contains
dipped in mercury and the end is brokcen open. On heating the tube, air but its temperature is not
some gas willbe expelled and on cooling, a small mercury pellet (M) Fig 3.8
altered.
is sucked inside which presses the remaining carbon dioxide gas into The apparatus having been set up, the screw-plungers are pushed
 PHYSICS
70 A HÀND BOOK OF DEGREE CQUATION OF STATE
71
into the cylinders to increase the pressure until the mercury pellets volume of the saturated vapour is now
smaller and that of the liquid
M and Mare just projected above the cylinders. The volumes greater than their respective values at
occupied by the gas and air are then read from the graduations on the hence densities are now 13.1'C, ie., their volumes and
approaching closer to each other.
that Secondly,
tubes A and A' respectively. As air is assumed to obey Boyle's law, the volumecorresponding to the point B' is less than
its pressure and hence the pressure on the gas in A is calculated from
the volume of air by the application of Boyle's law. Keeping the gas
to B which means that at increased
mass of temperature the volume
saturated vapour is becoming less at the time
corresponding
of agiven
at any desired temperature, the pressure on the gas is varied slowly Thirdly the pressure corresponding to the point C'is of liquefaction.
with the help of the plunger and in cach case, the pressure and the corresponding to the pount C whuch means thatgreater than that
at increased
corresponding volume of the gas are found out. Maintaining the gas temperature, increased pressure is necessary for complete liquefaction
at differcnt constant temperatures, several sets of readings of pressure of the gas, i.e., the compressibility of the gas and
and its corresponding volumes are taken. From these readings, P - the compressibility
of the liquid are approaching closer to each other.
V isothermals of carbon dioxide at different temperature are drawn. (iii) The isothermal at 31.1°C, however, shows no
The curves obtained by Andrews were of the form shown in fig. 3.8. like BC or BC which represents liquefaction of gas.horizontal portion
This means that
Interpretation of the curves : at this temperature the gas is not liquefied whatever may be the
(i)Considering the lowest isothermal i.e., the isothermal at 13.1°C, pressure
but the volume of the gas decreases regularly with increase of pressure
we sce that in the region AB, the volume decreases with the increase but more rapidly than is demanded by Boyle's law.
of pressure. This shows that carbon dioxide obeys Boyle's law as long (iv) The isothermals at 32.5°C and 36.5°C are of the same
as it remains in the gaseous state and this continues till the pressure form
as that at 31.1°C except that the region of large
increases to a value corresponding to the point B, after which the compressibility (the
liquefaction of the gas begins. Thc portion BC of the isothermal is regions like AB, A'B) is not very prominent and that the kink in the
curves is gradually less. The last isothermal at 48.1°C shows no kink
horlzontal which means the gas in contact with with the liquid is in at all and its shape becomes same as those of the so-called permanent
a saturated condition, its prcssure remaining constant and volume
diminishing as more and more gas is being liqueficd. At C, the whole gases obeying Boyle's law. In the top corner of the fig. 3.7, the
of the gas is liquefied. Since liquids are practically incompresible, any isothermals of air which is supposed to obey Boyle's law have been
further increase in pressure produced little diminution in volume. This shown separately. The similarity between air isothermals and carbon
is indicated by the portion CD of the isothermal which is almost parallel dioxide isothermal at 48.1°Cis striking.
to the pressure axis. The whole curve ABCD thus consists of three Significance of Andrew's experiment
portions viz. (i)the portion AB which represents the vapour phase of The first great significance of Andrews' experiment ies in the fact
the gas (i) the portion BC which represents the vapour and liquid that the highest temperature at which the slightest condensation of
phases in equilibrium (iiüi) the portion CD, which represents the liquid carbon dioxide vapournoticeable and the corresponding isothermal part
phase. becoming horizontal was 31C. This happens not only for carbon
(i) The isothermal at 21.5°C is almost similar in appearance to the dioxide but for all other substances. Thus for every substance we have
previous isothermal. The portion AB which is longer than AB, a temperature above which its vapour cannot be liquefied, however,
represents the vapourphase of the gas obeying Boyle's law, the portion great the pressure may be. This temperature is called the critical
B'C which is shorter than BC repsesents the vapour phase and the temperature. It is needless to mention that critical temperatures for
liquid phase in co-existence and the portion CD' representing the different gases are different. The isothermal at critical temperature
liquid phase. But the two isothermals have difference too. Firstly, the 1s known as critical isothermal. If the two ends of the horizontal
horizontal portion BC being shorter than BC, it is apparent that the portions of the isothermals are joined, almost a parabolic curve is
Obtained as shown by the dotted line in fig. 3.8. The point where this
 EQUATION OF STATE
72 A HAND BOOK OF DEGREE PHYSICS 73
Critical volume (V): The volume of 1 g of a
curve touches the critical isothermal is called the critical point. In fig. gas at
tempcrature and critical pressure is called the critical volume crilical
38, P is the critical point. According to the laws of mathematics, the of the
dP d'p gas.
Pont P is a point of inflexion, defined by the cond1tion dV dV? 3.6. Difference between a gas and a vapour
-0 In the region imited by the dotted lines, the vapour andthe liquid Ordinarily we do not make any difference betwecn a gas and a
co-cxist;on the right of it, the substance is in the state of unsaturated vapour; we use both the words in the same sense. But this is not
vapour and on the left the substance is completcly in the liquid state. correct. We should try to realise the difference betwcen the two.
The pressure coresponding to the point P is called the critical Erom Andrews' experiments we learnt that the vapour of a liquid
pressure and the specific volume of the substance (ie. the volume cannot be condensedIback into the liquid by the application of
pressure,
of one gram of the substance) at critical point is called the critical whatever be its magnitude, if the temperature of the vapour is above
volume. its critical tcmperature. For liquctacuon by pressure, the temperature
The second great significance of Andrew's experiment is that at of the vapour must be less than its critical temperature. For this
critical temperature, the propcrtics of the liquid and its saturated vapour onson, the aeriform state of a substance at a temperature above
become identical, the surface tension of the liquid vanishes and the the critical temperature is called the gas and below the critical
compressibility of the vapour increases enormously. temperature, a vapour. So the essential difference between a gas
The third grcat significance of Andrew's experiment is that it and a vapour lies in the fact that a vapour can be casily liquefied
liquidated the difference between the so -called permancnt gases and by the application of pressure but a gas cannot be. For liquefaction,
the easily liquefiable gases. The results of the experiment pointed out the temperature of the gas should be brought down below its critical
that the so-called permanent gases can also bc liqueficd if pressure temperature. Thus carbon dioxide at less than 31°C is a vapour and
be applicd on the gases, kecping the temperature of the gases below above 31°C, it is a gas.
thcir respective critical temperatures. Further, it should bc noted thát there is essentiaily no d1fference betwcen an
3.5. Definition of critical constants casily liqucfiable gas and a so-called pemancnt gas. All gascs can be liquefied by
the applicalion of pressure if their temperaturcs are below their respectve critcal
Critical temperature (T), critical pressure (P,) and critical volume temperatures Carbon dioxide is an casily liquefiable gas but it behaves like any so -callcd
(V)- these thrce quantities are known as critical constants of a gas. permanent gas such as oxygen, nitrogen or hydrogen and connot be liquefied by
Their definitions are as follows. the application of pressure if its temperature is made higher than iis cntical temperature
(31°C). Gases like hy drogen, nitrogen, oxygen etc. are regarded permancnt because
(i) Critical temperature (T): Critical temperature of agas is the they arc not casily liquefiable by pressure at ord1nary room temperature. their critcal
temperature being much below O°C.
temperature above which the gas cannot be liquefied, however, great
the applied pressure might be. Alternatively, it may be defined as the 3.7. Continuity of state
temperature at which the properties ofa liquid and its saturated vapour When a liquid evaporates, the change of state takes place from
become identical. the surface of the liquid. The vapour phase and the liquid phase
In the Celsius scale, the critical temperature for carbon dioxide is coexist with a surface of separation between the two. Never during
31°C (i.e. 304K), for oxygen - 118.8*C (i.e. 154K), for nitrogen the proccss of evaporation do we find the substance homogeneous:
- 147.1°C (ie. 125.9 K) etc. always it is heterogeneous being a mixture of vapour and liquid. t
is defined as
Critical pressure (P): The critical pressure of a gas may appear from this, that there is a discontinuity between the liquid
or a pressure just enough phase and the vapour phase of a substance.
the pressure corresponding to the critical point One of the far-reaching results of Andrews experiments is that
to liqucfy the vapour at the critical temperature.
example, is about 73 It negatived the above idea and established the continuity of state
The critical pressure for carbon dioxide, for between the liquid phase and the vapour phase of a substance.
atmospheres.
 DEGREE PHYSICS EQUATION OF STATE
74 A HAND BOOK OF
75
dioxide, at a volume are observed: (i) The densities of a liquid and its
Consider a given mass of a substance, say carbon vapour gradually
the point Bon the isothermal at 13.1C approach each other and finally become equal at the critical
and pressure representcd by is completely (i) the liquid loses its surface tension at the critical point (üi) point
(fig. 3.8). From the figure it is clear that the substance
above. If the gas be
The
in gaseous state under the conditions stated compressibility of the vapour increases very much as the critical point
pressure will
now hcated at constant volume, its temperature and isothermal is approached and becomes infinite exactly at the critical point.
substance crossing over the critical at We get some important information regarding the properties of
increase until the
31°C, attains a condition fepresented by the point G. The substance a substance near the critical point from the experiments of Callendar.
critical
may now be called 'gas' because its temperature is above the He took some pure water and drove out all dissolved air from
its
temperature. If the gas be now cooled at constant pressure, and found that the density of the water at 374C, the critical
temperature and volume will diminish until the substance attains a
temperature of water,, is not equal to the density of the aqueous
condition representcd by the point H on the isothermal ABCD at vapour. Carefully experimenting with such water, he found that the
13.1°C, having crossed the critical isothermal once again. In this difference of densities continued up to a temperature of 380°C. From
condition, the substance is clearly in the liquid state. We thus see this it is supposed that the critical point is not exactly a point but
that the gas has been changed from the gaseous phase represented extends over a certain region. So, instead of critical point, it should
by the point B to the liquid phase represented by the point H but be called a critical region.
nowherc did any discontinuity occur, Le., nowhere did the substance 3.9. Vander Waals' equation of state for real gases
exist simultaneously in two phases. Now, when the substance is in
the liquid phase represented by the point H, we can come to the Results of Amagat'sexperiment proved that realgases do not behave
point C on the same isothermal by simply lowering the pressure. according to Boyle's law and the deviation increases as the temperature
At this point, the pressure and temperature of the substance arc of the gas approaches the critical temperature. Andrews' experiment,
same as those at the point B but the substance is now in liquid on the other hand established that bya continuous process, a substance
phase instead of vapour state. can be transformed from its gaseous phase to the liquid phase. The
So, by the above continuous process, a given mass of vapour is ideal gas equation PV = RT cannot explain this behaviour of real
first converted into gas and then into liquid at the same initial gases. In 1879, Vander Waals, with a realistic view conforming to
temperature and pressure and in no stage, the homogeneity of the the behaviour of real gases and rejecting some of the earlier simplifying
substance is disturbed. This is known as the continuity of state. From assumptions made during the deduction of ideal gas equation from
this Andrews rightly concluded that ' the liquid and the gaseous stales kinetic theory, established a new equation of state for real gases.
of a substance are only the distant stages of a long series of continual It may be pointed out here that while deducing the ideat gas equation
physical changes'. In a simple way it may be stated that the liquid from kinetic theory it was assumed that (i) the molecules of a gas
and gaseous states are just different forms of essentially the same are all point masses and occupy negligibly small volume compared
condition of matter. For this reason, at high temperature and low to the total volumne occupied by the gas and (ü) no force of attraction
pressure, a substance behaves like an idcal gas and obeys Boyle's acts between the molecules. Vander Waals expressed doubts about
law but with the fall of temperature and increase of pressure, the the validity of these two assumptions and argued that gas molecules
substance deviates more and more from Boyle's law and gradually had finite size instead of being point masses and that the molecules
acquires the property of liquid at the cost of the properties of gas. Cxerted a force of attraction among each other. He made suitable
Finally when the temperature is sufficiently low and pressure very corTections in the following way on these two points and established
high, the substance becomes completely liquefied. the famous equation of state, known as Vander Waals' equation
of state for real gases.
3.8. Properties of a substance near the critical point
Near the critical point, the distinction between the properties of i) Correction due to the finite size of the molecules :
a liquid and those of its vapour vanish and the following properties Consider a closed space PQRS having volume V and containing
 DEGREE PHYSICS EQUATION OF STATE 77
HAND BOOK OF
A
76 inside the space PORS such that its sphere of influence falls completely inside the
molecule Ais moving 3.110). The molecule A will be attracted equally in
some gas. Suppose, a gasthe sake of understanding the matter, we space (fig. all
PO. For directions by the surrounding molecules residing in the sphere of
in the direction molecules to be tiny
elastic spheres of diameter
influence sothat the net force acting P
shall Supposethe gas d. [fig. 3.9]. Let the molecule
and on the molecule A may be taken to
collide against the wall OR
rebound along the same path, F be zero. But when the molecule
reaches the point B near any wall,
B PO = SR = , then for a complete
journey, ie., starting from the wall it will feel a resultant force inward.
PS and back to it after being The same is true for all other
rebounded by the wall QR, the molecules approaching the wall. The
distance travelled by the molecule is velocity and hence the momentum of
not 2/ but 2(! - d), [for, the the molecules colliding against the
centres of two colliding molecules walls will, as a result of this inward S R
R attraction, be reduced. Fig 3.10
cannot come closer to each other than
Fig. 3.9
adistance equal to the diameter of Consequently, the pressure exerted by the gas on the walls of the
motion of all the molecules of the container is a little less than it would have been in the absence of
the either]. If we consider the inter-molecular attraction.
volume available for the movement
gas, we see that the effective
total volume Vof the container It is clear that the diminukon in pressure depends on (i) the number
of the molecules is less than the
the whole volume V will not of molecules attracting.baek per unit volume and (iü) the number
So, with the increase of pressures, deducing the
diminish (this had been supposed to be the case in (V-
of molecules striking unit area per unit time on the walls of the
place in a volume
ideal gas equation) but the diminution takes fraction
vessel. Each of the factors depends again on the number of molecules
represents a small
b)which is slightly less than V. Here, b' per unit volume, i.e., on the density of the gas.
whatever may
of the volume which will never underg0 compression, So, the diminution in pressure cc (density of gas)' c
evidently related to the total volume
be the pressure. The constant b is
called the co-volume. where 'a' is the constant of proportionality. Hence, actual pressure
of the gas-molecules and is
(iüi) Correction due to inter-molecula attraction : = P+, where P is the observed preSsure.
Inter-molecular attraction in gases is supposed to be very much
like the inter-molecular attraction in liquids for which the liquids Thus putting ( V - b) instead of V and
tension. This instead of P in
are known to exhibit the phenomenon of surface
attraction obviously depends on the distance between two molecules the ideal gas equation, we get
but it is entirely different from gravitational attraction. The
inter-molecular forces become predominant when the distance |P+v- b) =RT
between two molecules is very small but becomes negligible when
the distance is large. Hence, for every molecule, we can imagine This is Vander Waals' equation of state for real
gases. The constants
a sphere of influence such that whenever another molecule enters a and b appearing in the equation are
known as Vander Waals'
the sphere of influence of one molecule, only then the two molecules constants. The units of a are atom-ltre/mole and that for b
will exert a force of attraction upon each other. are
Suppose there is a molecule A well inside a closed space
litre/mole.
3252-6
 EQUATION OF STATE 79
DEGREE PHYSICS
78 AHAND BOOK OF
CDarc similar in both scts
equation vapours. Beside, the portions AB and
3.10. Discussion on Vander Waal's of the curves.
From Vander Waals' cquation wc get, curve no 2 represcnt thc
(iv) The three points B, F and Cin
|(V-b)- RT () the curve no. I is coK erned,
threc real roots of cqu. (i) So far as Considering the jsothenals
the wavy portion is somewhat extended
the portion BCis gradually
or, (PV+ a)(V - b)- V'
RT at hiher tcnperaturcs, we sce that of volune arc
shortcning which mcans that the threc rcal roots
RT y'+v. 0 (u) critical isothemal (ie., at
P approaching closcr to cach other. At the roots
the valucs of the three
(u) is a cubic cqualion 31.1C) represented by the curve no 3,
For a given value of P and 7, the cqn. coincide with the critical point P Above crilical temperature, we
in volume V Solving the get only one rcal root of V for a given value of P
above cquation, wc get thrce D
It may, therefore, be said that Vander Waals' cquation, in general,
valucs of V, all of which may 1 234 represents the behaviour of a real gas.
be rcal or onc of them rcal
and the other two imaginary. 3.11. Inter-relations between Vander Waals' constants, critical
P
For agiven gas, if the valucs and Boyle temperatures:
of the constants a and b are (a) Critical constants in terms of Vunder Waals' constants :
known, then for a particular 491'C Rewriting Vander Waals' cquation according to the cqn. (u) of art
d1fferent B RT ab
temperature, 31 I'C 311, we have, V' - v2 b+ + V. P
i) - )
values of P may be found A P
This is a cubic cquation in volume V For given valucs of P and T
R
out from the above cquation 131C
corresponding to different the yolume V will have thrcc roots which will rcduce to one single
valucs of V. Hence we may root at the critical point.
draw P V isothermals at Suppose the valuc of the critical volurne = x ; So V= x or (V - x)'
d1fferent tempcratures for -0 or V- V'.3x + V. 3x- ' 0 (u)
the given Such
gas.
isothermals are known as Fig 311 Comparing the co-cffccients of V', V and Vin thc cqns (i)and
RT ab
Vander Waals isothe (u), we get, 3x= b+ .. (ui)3x'4
- . . (iv) and x'= .. (v)
at d1fferent p P
rmals Fig. 3.11 shows Vander Walls' isothermals ab
lemperatures for carbon dioxide. Dividing cqu. (v) by cqn. (iv) Pb. x =3b.
Fig 3.8 on page 69 shows the
isothermals obtained by Andrews 3 P
theoretical curves obtaincd
from experimental results. Comparing the expcrimental curves of Hence, critical volune |V=3b (A)
from Vander Waals' cquation with the
Andrews we may make the following remarks: Putting this valuc of x in eqn. (iv), we get 3x9b' ~or P 2752
between the two sets of
() There is a good general agrcement
curves.
scts of isothermals arc identical.
a
Hence, critical pressurc, P=
(n)At high temperatures, the two (B)
31.1'C are wavy. BEFC is 2762
(um) Some portion of the curves below the
2. But in Andrews' curves,
such a wavy region in curve no. condensation of Putting thc values of x and P in cqn. (ii), 3 x3b=b+K27b2
representing
corTespond1ng regons are horizontal
 EQUATION OF STATE 81
DEGREE PHYSICS
A HAND BOOK OF
80 eqn. (ii),
8a
Substituting this value of V in
or, 8a = 27 b.R. T or, T = 27R.b 2a =
RT. or, T. =
8a
27 R.b
276 4b?
8a in egn. (i),
Hence, critical temperature, 27R.b
(C) Substituting the values of V and T,
Rx 8a a
=.P, =
(fig. 3.7) is a point
Alternative method: As the critical point P dotted P,= 27.R.b x 2b 9b? 27b
point of the curve RPQ in critical constants :
of inflexion as well as the maximum (b) Vander Waals constants in terms of
fig 3.12. we get, 8a
dP We have seen that P,C = and T, =
= 0.
27b 27R.b
dV dv
8a 27b2 8b
|(V - b) = RT
Now, Vander Waals' equation gives P+ v Dividing we get, P 27R.b R
RT (i) RT, RT,
or, P = = 0.125. (D)
V -b b =
8P. P,
Differentiating eqn. (i) with respect to V, we get,
aP RT 2a (ü) T 64a' 27b? 64a
+ Again, X

dV (V - b)' P. (27)'R².b² 27R

dP
At critical point, 0, T = T, and V = V. 27 R'T2
dV R²T,
RT. a = = 0.42 (E)
RT. 2a =0 or, 2a (ii) 64 P, P.
+
(V,- b) v (V,- b)²
(c) Boyle temperature in terms of Vander Waals' constants :
Differentiating eqn. (i) again with respect to V, we get, RT
2RT 6a
We know, |PV- b) =RT or,. V - b

dy2 (V- b) PV =
RTV a
V - b
At critical point, . = 0, T = T, and V= V, Now, at Boyle temperature (i.e, when T = T¡) a real gas obeys
the idcal gas equation even if the pressure is high and we can write,
PV = R.TR
2RT. 6a
=0 or,
6a 2RT: (iv)
v V (V, - b) .:. R.T=
RTV a RTb a
(V,- b) Or, RT, Or,
V-b V V-b V
Dividing eqn. (ii) by the eqn. (iv) we get,
a(V- b) a
V,- b (F)
or, V, = 3b R.b.V. R.b
3 2
(Neglecting b in comparison with V)
 PHYSICS EQUATION OF STATE 83
OF DEGREE
82 A HAND BOOK
equation of state
tor ditterent rcal gases, the
Since a and b have different valucs different gases. 3.14. Law of corresponding states: Reduced
bc expressed
for If the actual pressure, volume and temperature of a gas and critical
Boyle temperature is also different as fraction of its critical pressure, critical
volume
of critical temperature : these thrce
(d) Boyle temperature in termsa_27 temperature respectively, then the cquation connccting the reduced
known as
We know, T,=
8a
or, T, provides us an important equation of statc, of state
27R.b R.b 8
equation of state. The characteristic of the reduced equation
is that it is true for all gases. Vander Waals'
27.T,= 3.375 T, (G) To cstablish thc reduced cquation of state from
T¡= 8 follows:
cquation, we are to procccd as
3.12. Critical coefficient According to Vander Waals' equation, we have,
R.T, coefficient. For an ideal gas, - b) = RT .. (i)
The term is known as critical (V
P,V, For a real gas obeying
its value is 1; but for a real gas it is not so. Let P = nP; V= . V, and T = 0T Here we have expressed
can find the value of the critical
Vander Waal's equation, we the actual pressure, volume and tempcrature of the gas in terms
coefficient in the following way: of its critical pressure, critical volume and critical temperature
RT, =RX 8a 27b 1_8 =2.66. respectively. n, and are mere numbers (i.e., fraction). Substituting
X
35
these values in equation (i) we get,
P,V. 27 R.b
It is a pure number and is independent of
the constants a and b. (4 V,- b)= R.0.T
3.13. Limitations of Vander Waals' equation
governing the hehaviour 8a
The equation put forward by Vander Waals = 3b and T. =27 5.R
a

equation. But we know, P,= 2762

of actual gases is, no doubt, the most useful and satisfactory
follows:
Still it has some limitations. They are as (Sec art 3.12 (A), (B) and (C)]
for a gas. But
(i) Vander Waals assumed a and b to be constant
to different
experimental detemination of the constants, according method, 8a
yields different values. Even by the same the So, (436 - b) = R.0.
methods, 2762 27 b.R
temperatures.
constants are found to have different values at different
in the cquation.
This shows that there is some foundamental drawback 80
correct, the critical coefficient
(ii) If Vander Waals equations is or,
27
and it will be equal to 2.66. But,
for all real gases should be same varying
in reality, the value is found to be different for different gases,
of 3.28 to the highest value of 4.99. For
from the lowest value
according to Vander Waals'
or, t+(34 - 1) =80 Libra

no gas, values come below 3 whereas

equation, it should be 2.66.
(ii) According to Vander Waals' equation V,
determination of critical
varying from 1.4 b to 2.8b.
volume

(iv) T¡ = 3.375 T,according to Vander

of different
= 3b. But actual
gases yields results

Waals' equation. But

Momis
(iü)
This equation is known as the reduced equation of state. Note that
T< 3.3 T this equation is free from the gas constant R or the Vander-Waals'
cxperimental results show that for most of the gases,
 DHGREEPHYSICS HQUATION OF STATE 85
AHAND BOOK OF
appiicable to any pas RT,
constants a and h The cquation is, thkrclore, known as reduced V, 2b and P V. 369 So Dietena's cquation agrecs with the expennental
are
With the same valucs of n, and , which Van- der Waal's or Clasius's cquation
results bctter than
Miakes of staie wSaha and Bose cqualion Bavcdujon themodynarmics, an cquation was proposed
Prof SN Bose The cquation is as follows
" Law of Corresponding State : by Prof M N Saha and
of state thal if two RT (V- 26)
I tollows from the above reduced cquation they will also
P
26
RT log
and volune,
ases have the sane reduced pressure known as the law of
Erom this cqualion, the value of critical cocfficicnt comcs out as 353 and agrees
have the same reduced temperature This is fairly wellwith cxpeimental results
law may be stated as follows:
corsponding states In general the reduced " SOLVED PROBLEMS
same values for any two of the
When twO guses have
suriales 1, 4 and 0, they will also hae the same alue for 1. Assuming I atmosphere and 1 cm as the units of pressure
the thård ariable In such cases the two gases are said
to be in and volume respectively at 0C, Vander Waals found for CO, a -
corresponding states 0.00874 atmosphere and b= 0.0023 cm'. Calculate the critical values
of temperature, pressure and volume for CO,. (Burd. U. 1995]
3.15. Some other equations of state: Ans. From Vander Waals' cquation, we can write
Although Van der-Waals' cquation of state succcdcd in cxplainng many aspects
shortcomings Realising the defeets
o the behaviour of rcal gascs, yet, it had sone
the cquation |Pv-b) - RT
a

of Van-der Waals cquation, mauy scicnticts, in later ycars, studicd gascs Some v
of state in depth and suggested morc accurate cquatiens of state for rcal
of the mportant cquations of state are inentioncd bclow 0 00874) 1.00874 x 0.9977
) Aameringh Onnes' equation: K Onnes rcaliscd that an cquation of state |(1-0.0023) =Rx273 .. R=
cquation, so, 273
sutatsle to cxpress the bchaviour of rcal gases must not be a closcd
he proposcd an cquatien in the form of a serics cxpansion containing a large number
of coefcents as foliows 8a 8 0.00874 x 273
Now, 305.5K.
PV A+ BP + CP +DP + 7 Rh 27 0.0023 x 1.00874 x 0.9977
where A, B. C ct arc constants of gradually diminishing valuc These constants
are knewn as Viral coxfficenS. In Celsius scale, , = 305.5 - 273 = 32.5'C.
is inverscly
n} Causius' s equaion Assuming that the intermolecular force in a pas
proportional to the absolute temperature of the gas, Clausius modificd Van- der-Waals Also, P,=
a 0.00874
= 61.2 atmospheres.
equation and proposcd the following cquation of state 27b 27 x (0.0023 )²
(V- 6)- RT
|P+
T(V + c) And V, = 3b = 3 x 0.0023 = 0.0069 cm
In this cquation, four constants are involved and for this rcason, its agrccment 2. For CO, gas, a = 7074 x 10°; b = 1.881 x 10 cm and
wth the Cxperimcntal results is possibiy more marked
im) Bernherlo' s equation : Replacing the constant a of the Van
-der-Waals' R 3.663 x 10 /k calculate the critical temperature for CO,.
cquaion by Berthelot suggestcd the folowing cquation [C.U. 1997]
8 a
b)= RT Ans. T, = Putting the values given,
27 R.b
results for ord1nary 7.074 x 10-9
he ahove cqualion agrccs very well with the cxperimental T,
pressre taigig wpto about five atrnospheres theoretical
27 3.663 x 10- x 1.881 x 10
(v) Detenct cquauon The cquation Dicterici proposcd from a = 304.2K
discuseon is as ollows
PIV- b) RTe Ak, where A s a constant From this cquations we get In celsius scale T, = 304.2 - 273 = 31.2C.
86 A HAND BOOK OF DEGREE
PHYSICS EQUATION OF STATE 87

3. Calculate Vander Waals' constnats a and bfor dry air, given dP RT 2a

0 (i)
Now,
that P = 37.2 atmospheres and T, = 132 K and R per mole dV (V - b)? TV
82 x 10 m' atmos K'. d'p 2RT 6a
=0 (iü)
and
27 R'T? and 1 R.T, dy2 (V - b) TV*
b
Ans. We know, a =
64 P. 8 P. At critical point, V= V,; P= P,and T = T,
have
Substituting the values, we get, From cq " (1) and (ü), we
27 (82 x 10°) x 2a(V,- b?
a =
64
X
37.2
(132)132 x 10 atmos. m RT +
2a
=0or RT,=
(V,- b)' T,V) T,V}
82 x 10x 132
and b =-x =363 x 10- m3
8 37.2 2 RTe 6a
3a(V,- b)
L=0 or RT,= - (1v)
4. Show that vander Waals' equation of state is only a first and,
T,V
approximation of Dieterici' s equation : (V- b TV
Ans. Dicterici's equation: P.e/RTV (V - b) = RT and 2a(V,- b)' 3a(V, - b) .. V, = 3b
a
Vander Waals' cquation: P+(v - b) = RT TV? T.V:
v
2a (3b - b)? 8a
Now, e= | + x +
1x 2
From cq (iü) RT=
T. x 27b? :.T=121 Rb
Retaining first two terms and neglecting others, if the above relation
is applicd to Diaterici's equation, we get, Again Berthelot's cquation at critical point is
aP RT, R 8a 27 Rb
Pea/RTV a_= P+RTV
RIV
= P+ (:. PV = RT) P,=
a
26V 27 Rb 96 8a
V,- b T,V.
a
So, Diaterici's cquationreducesto |P +V- b) =RT which 2 aR
12b Y 3b
is Vander Waals' equation.
QUESTIONS
5. Using Berthelot 's equation of state |P + (V- b) =RT,
show that the critical constants are given by :
T " Essay type:
1. Explain the behaviour of carbon dioxide, nitrogen and
hydrogen under high
(C.U. 1953 ]
pressures and d1scuss the val1d1ty of Boyle's law for h1gh pressure.
2 aR 8a on Boyle's law at high pressure. Mention
V=3b and I=27Rb [C. U. (Hons) 1980] 2. G1ve an account of Amagat's experiments
P26 36
Ans. Bertholet's equation of state can be written as,
the conclusions drawn from the experiments,
3. Give a bricf account of Andrews' experiment on the
(C. U. 1939 )
isothermals of carbon dioxide
and show with the help of these isothermals that the gaseous(C.andU.liquid forms are
RT (Hons.) 1965 1
P= only d1stant stages of physical changes of a substance.
mention the
V- b T.V 4. GIve an account of Andrews' experiment on carbon dioxtde and
siguificance of the results of the expenment.
r=0 and also =0. 5. State Vander Waals' cquation of state for a rcal gas. How do you butld up
At critical point from it a reduced equation of state applicable any gas? [C. U. 1995]
ldve7