An equation which shows relation between pressure, volume and temperature of a given

mass of a homogenous substance is called equation of state.

PV=RT
High temp; low pressure
Equation of State
A more general form is proposed by K. Onnes
𝑃𝑉=𝐴+𝐵𝑃+𝐶𝑃2+𝐷𝑃3
A, B, C, D are constant depending on nature of gases and temperature
𝐴𝑡 𝑙𝑜𝑤 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑃→0, 𝑃𝑉=𝐴=RT
𝑃𝑉=𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑑/𝑑𝑃 (𝑃𝑉)=0
𝑑/𝑑𝑃 (𝐴+𝐵𝑃+𝐶𝑃2+𝐷𝑃3)=0
𝐵+2𝐶𝑃+3𝐷𝑃2=0
𝐴𝑡 𝑙𝑜𝑤 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑃→0, 𝐵=0
The temp at which B = 0 is known as Boyle temp, 𝑇𝐵.
At low temperature, B is negative and increase to zero with increase of temperature and
become positive with further increase of temperature.

Regnault

Discussion of Andrew’s Results (Study from Book)!!!

The point C on the critical isothermal where liquid,
vapor and gaseous states of a substance meet is
described as the critical point.
Scientific difference between vapor and gas
Van der Waal’s equation of state:
𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2

Assumptions:
1. Gas molecules have finite size and cannot be regarded as point masses.
2. Molecules attract one another with a weak force which depends only
upon the distance between them.
3. The number of collisions with the walls of the container are the same for
point and finite sized molecules.
4. The molecular density is small.
1. Correction for finite size:
Consider one mole of a gas enclosed in a container of volume V. If the gas
composed of point masses, all this space could be available to them for free
motion. When molecular size is considered, the volume available to a single
molecule for free movement will be less than V. Let us denote the reduction by
b. This is called the co-volume and depends on the nature of the gas. Therefore,
the factor V occupying in the perfect gas equation would be replaced by V-b. For
1 mol of the gas we have P(V-b) = RT. The magnitude of b is equal to four times
the total molecular volume for 1 mol of a Van der Waal’s gas.
Let the radius of each molecule is r. At the instant of collision, the center-to-
center distance of the two colliding molecules will be d=2r as shown in Figure.
4
This implies that around any molecule a spherical volume 𝑉𝑠 = 𝜋𝑑 3 will be
3
denied to every other molecule. This volume is called the sphere of exclusion
4 4
and is eight time the volume 𝑉𝑚 = 𝜋𝑟 3 of a volume, i.e., 𝑉𝑠 = 𝜋(2𝑟)3 =
3 3
4 3
8 × 𝜋𝑟 = 8𝑉𝑚 .
3

Let us imagine filling the container with n molecules one by one. Then
Volume available to the first molecule = 𝑉
Volume available to the second molecule = 𝑉 − 𝑉𝑠
Volume available to the third molecule = 𝑉 − 2𝑉𝑠
And by induction volume available to the Nth molecule = 𝑉 − (𝑁 − 1)𝑉𝑠
Hence the average volume available to each molecule is,
𝑉 + (𝑉 − 𝑉𝑠 ) + (𝑉 − 2𝑉𝑠 ) + ⋯ + (𝑉 − (𝑁 − 1)𝑉𝑠 )
=
𝑁
𝑁𝑉 𝑉𝑠 𝑉𝑠 𝑁(𝑁 − 1)
− (1 + 2 + ⋯ + (𝑁 − 1)) = 𝑉 −
𝑁 𝑁 𝑁 2
𝑉𝑠 (𝑁 − 1)
=𝑉−
2
For large N, we can neglect 1. Therefore,
𝑁 𝑁
𝑉̅ = 𝑉 − 𝑉𝑠 = 𝑉 − (8𝑉𝑚 ) = 𝑉 − 4𝑁𝑉𝑚 = 𝑉 − 𝑏
2 2
(𝑃)(𝑉 − 𝑏) = 𝑅𝑇

2. Correction for the intermolecular attraction:

To account for intermolecular attraction, we invoke assumption 2.
A molecule in the interior of the gas is, on average, attracted equally in all
directions. So, there is no resultant force on it. However, this is not true for a
molecule in the outermost layer close to the surface. There will be a net inward
force. So, whenever a molecule strikes the walls of the container, the
momentum communicated will be less than that for an ideal gas. Thus, we find
that intermolecular forces result in decrease in pressure. This drop is known as
cohesive pressure. The cohesive pressure is proportional to the number of
molecules per unit volume in the surface layer (on which the inward force act)
and the number of molecules per unit volume in the layer just below the surface
layer (which are pulling the striking molecules due to attraction).
𝛼 ′ (𝑁𝑚)2
Therefore, 𝛥𝑃 ∝ (𝜌)2 ⇒ 𝛥𝑃 =
𝑉2

where, 𝛼 ′ is the proportionality constant.

𝑎
If we put 𝑎 = 𝛼 ′ (𝑁𝑚)2 , 𝛥𝑃 =
𝑉2

Hence, in the ideal gas equation we must replace P by the sum of the observed
pressure and the drop caused by the intermolecular force/attraction, i.e.,
𝑎
(𝑃 + 𝑉 2 ). Therefore, the Van der Waal’s equation of state is,
 𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2
Critical Temperature:
It is the highest temperature for a gas at which the gas can be liquefied by
increasing pressure only; above this no liquefication is possible.
Critical pressure:
The pressure required to liquefy the gas at critical temperature is called critical
pressure.
Critical Volume:
The volume occupied by one gram molecule of the gas at the critical
temperature and critical pressure is called critical volume.
Critical constants in terms of a and b:
According to Van der Waal’s equation of state
𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

When a graph between P and V is plotted for different constant values of T, a

set of isotherms is obtained as shown. The isotherm at critical temperature is
horizontal at point R. Therefore, at R, dp/dv must be zero.
Also, we see that curvatures of these isotherms are opposite in two sides of
point R. This point is called the point of inflexion or critical point. The critical
temperature and corresponding values of pressure and volume at critical point
ⅆ2𝑃
R, are called the critical constants. Therefore, at R, = 0.
ⅆ𝑉 2

Critical parameters of Van der Waal’s equation of state:

According to the Van der Waal’s equation of state,
𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑅𝑇 𝑎
𝑃 = 𝑉−𝑏 − 𝑉 2 (1)

𝑑𝑃 𝑅𝑇 2𝑎
⇒ =− +
𝑑𝑉 (𝑉 − 𝑏)2 𝑉 3
𝑑2𝑃 2𝑅𝑇 6𝑎
⇒ = −
𝑑𝑉 2 (𝑉 − 𝑏)3 𝑉 4
ⅆ2𝑝
At critical point, = 0, 𝑇 = 𝑇𝑐 , 𝑉 = 𝑉𝑐
ⅆ𝑣 2

2𝑅𝑇𝑐 6𝑎
− =0
(𝑉 𝑐 − 𝑏)3 𝑉𝑐4
6𝑎 2𝑅𝑇
⇒ 𝑉 4 = (𝑉 −𝑏𝑐)3 (2)
𝑐 𝑐
ⅆ𝑃
At critical point, = 0, 𝑇 = 𝑇𝑐 , 𝑉 = 𝑉𝑐
ⅆ𝑣

−𝑅𝑇𝑐 2𝑎
+ =0
(𝑉𝑐 − 𝑏)2 𝑉𝑐3
2𝑎 𝑅𝑇
⇒ 𝑉 3 = (𝑉 −𝑏𝑐 )2 (3)
𝑐 𝑐

(3)/(2)
𝑉𝑐 𝑉𝑐 − 𝑏
=
3 2
⇒ 𝑉𝑐 = 3𝑏
Substituting the value of VC in (3)
 2𝑎 𝑅𝑇𝑐
=
(3𝑏)3 (3𝑏 − 𝑏)2
2𝑎 𝑅𝑇𝑐
⇒ =
27𝑏3 4𝑏 2
8𝑎
⇒ 𝑇𝑐 =
27𝑏𝑅
Substituting the value of TC and VC in (1)
𝑅 8𝑎 𝑎 𝑎
𝑃𝑐 = ⋅ − 2=
3𝑏 − 𝑏 27𝑅𝑏 9𝑏 27𝑏 2

Critical coefficient of Van der Waal’s constants:

1. 𝑉𝑐 = 3𝑏
𝑎
2. 𝑃𝑐 =
27𝑏2
8𝑎
3. 𝑇𝑐 =
27𝑅𝑏

From (3) and (2)

𝑇𝑐2 8𝑎 2 27𝑏 2 64𝑎
=( ) × =
𝑃𝑐 27𝑅𝑏 𝑎 27𝑅2
27𝑅2 𝑇𝑐2
=> 𝑎 =
64𝑃𝑐
Diving (3) by (2)
𝑇𝑐 8𝑎 27𝑏2 8𝑏
= × =
𝑃𝑐 27𝑅𝑏 𝑎 𝑅
𝑅𝑇𝑐
⇒𝑏=
8𝑃𝑐
𝑅𝑇𝑐 8𝑎 27𝑏 2 1 8
=𝑅× × × = = 2.67
𝑃𝑐 𝑉𝑐 27𝑅𝑏 𝑎 3𝑏 3
Which is a numerical constant and is independent of the characteristic constants
a and b of the gas. This constant ratio is known as the critical coefficient whose
value is expected from the above consideration to be 2.67 for all real gases. But
the value of this constant varies from gas to gas and the average value comes
nearly 3.75. For helium it is 3.27.

Reduced equation of state or law of corresponding states:

The Van der Waal’s constants a and b depend upon temperature as well as the
nature of the gas. It is therefore desirable to eliminate them and put Van der
Waal’s equation in the form that is applicable to all gases. To do so let is define
𝑃
𝑃𝑟 =
𝑃𝑐
𝑉
𝑉𝑟 =
𝑉𝑐
𝑇
𝑇𝑟 =
𝑇𝑐
Where P, V and T are the actual pressure, volume and temperature of a gas and
PC, VC, and TC are the critical pressure, volume, and temperature, respectively.
Pr, Vr, and Tr are the dimensionless number. These are known as reduced
variables of state. The Van der Waal’s equation of state is,

𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2
𝑎
(𝑃𝑟 𝑃𝑐 + 2 2 ) (𝑉𝑟 𝑉𝑐 − 𝑏) = 𝑅𝑇𝑟 𝑇𝑐
𝑉𝑟 𝑉𝑐
𝑎 1 𝑅𝑇𝑐
(𝑃𝑟 + ) (𝑉𝑟 − ) 𝑉 = 𝑇
𝑉𝑟2 𝑉𝑐2 𝑃𝑐 3 𝑐 𝑃𝑐 𝑟
𝑉𝑐
𝑏=
3
27𝑅2 𝑇𝑐2 1 1 8
(𝑃𝑟 + ⋅ 2 2 ) (𝑉𝑟 − ) = 𝑇𝑟
64𝑃𝑐 𝑉𝑟 𝑉𝑐 𝑃𝑐 3 3
 𝑅𝑇𝐶 8
=
𝑃𝐶 𝑉𝐶 3
27 𝑅𝑇𝑐 2 1 1 8
(𝑃𝑟 + ( ) ⋅ 2 ) (𝑉𝑟 − ) = 𝑇𝑟
64 𝑃𝑐 𝑉𝑐 𝑉𝑟 3 3
27 64 1 1 8
(𝑃𝑟 + × × 2 ) (𝑉𝑟 − ) = 𝑇𝑟
64 9 𝑉𝑟 3 3
3 1 8
(𝑃𝑟 + ) (𝑉𝑟 − ) = 𝑇
𝑉𝑟2 3 3 𝑟
This equation is known as the reduced equation of state or the law of
corresponding states, in that if any two of the variable’s Pr, Vr, and Tr are the
same for two different substances, the third will also be the same for them (and
the states of gases will correspond to each other).
Pros and cons of Van der Waal’s equation of state:
Pros:
1. Van der Waal’s equation holds good for all real gases till moderately high
pressures.
2. Van der Waal’s equation represents the trend of the isotherms representing
the variation of PV with P for various gases.
3. Using Van der Waal’s equation, it is possible to obtain an expression of Boyle
temperature, Critical constant, and inversion temperature in terms of Van der
Waal’s constants.
4. Van der Waal’s equation is useful in obtaining a “reduced equation of state”
which obeying a general equation of state has advantage that a single curve can
be obtained for all gases by plotting the variables if the equation is graphically
represented.
Cons:
Although Van der Waal’s equation is applicable generally over a wide range for
variety of substances, but it has its own limitations. Its main draw backs are as
follows:
1. The value of a and b are not constant for a gas., Their values obtained
experimentally (even by a single method) vary with temperature.
2. Average experimental value of critical volume is found to be 2b, varying from
1.4b for argon to 2.8b for hydrogen while its value was found 3b.
𝑅𝑇𝑐
3. The value of critical coefficient (=1 for perfect gas) is found to be 3.7 on
𝑃𝑐 𝑉𝑐
average, varying from 3.28 for hydrogen to 4.99 for acetic acid while it should
be (8/3=) 2.67 for all gases according to Van der Waal’s equation. Therefore, it
seems to depend on molecular structure of gas.
4. According to Van der Waal’s equation Boyle temperature comes 3.375 TC. For
helium it is 3.65 TC and for other gases below 3.3 TC