Equation of state

By
Dr. Suha Shayla Abdul-Hassan

States of Matter:
Gases, liquid and crystalline solid are the three primary state of matter or phase. Solid
with high vapor pressure, such as iodine and camphor, can pass directly from the solid
to the gaseous state without melting at room temperature. This process is known as
sublimation

The Gaseous State

a pressure → a force per unit area → expressed in 𝑑𝑦𝑛𝑒𝑠 ⁄𝑐𝑚2.Pressure is also
recorded in atmospheres or in millimeters of mercury Another important
characteristic of a gas, its volume, is usually expressed in liters or cubic centimeters
(1 cm³ = 1 mL) The temperature involved in the gas equations is given according the
absolute or Kelvin scale. Zero degrees on the centigrade scale is equal to 273.15 Kelvin
(K).

1
The Ideal Gas Law
the gas laws formulated by Boyle, Charles, and Gay-Lussac an ideal situation where
no intermolecular interactions exist and collisions are perfectly elastic, and thus no
energy is exchanged upon collision. Boyle's law relates the volume and pressure of a
given mass of gas at constant temperature,
𝟏
𝑷𝜶
𝑽

or 𝑷𝑽=𝑲 (2 _ 2)

The law of Gay-Lussac and Charles states that the volume and absolute temperature
of a given mass of gas at constant pressure are directly proportional,

𝑷𝜶𝑻
𝑽=𝑲𝑻 (2 _ 3)

These equations can be combined to obtain the familiar relationship

𝐏𝟏 𝐕𝟏 𝐏𝟐 𝐕𝟐
= (2 _ 4)
𝐓𝟏 𝐓𝟐

In equation (2-4), 𝑃1 , 𝑉1 , and 𝑇1 are the values under one set of conditions and
𝑃2 , 𝑉2 , and 𝑇2 the values under another set.
Example (2-1)
The Effect of Pressure Changes on the Volume of an Ideal Gas

In the assay of ethyl nitrite spirit, the nitric oxide gas that is liberated from a definite
quantity of spirit and collected in a gas burette occupies a volume of 30.0 mL at a
temperature of 20°C and a pressure of 740 mm Hg. Assuming the gas is ideal, what is the
volume at 0°C and 760 mm Hg? Write

Answer//
𝟕𝟒𝟎×𝟑𝟎 𝟕𝟔𝟎 × 𝑽𝟐
= → 𝐕𝟐 = 27.2 ml
𝟐𝟕𝟑+𝟐𝟎 𝟐𝟕𝟑

2
From equation (2-4) it is seen that 𝑷𝑽⁄𝑻 under one set of conditions is equal to
𝑷𝑽⁄𝑻 under another set, and so on. Thus, one reasons that although 𝑷, 𝑽, and 𝑻 Change,
the ratio 𝑷𝑽⁄𝑻 is constant and can be expressed mathematically as

𝑃𝑉
=𝑅
𝑇
or 𝑷𝑽=𝑻 (2 – 5)

in which 𝑹 is the constant value for the 𝑷𝑽⁄𝑻 ratio of an ideal gas. This equation is
correct only for 1 mole (i.e., 1 g molecular weight) of gas; for 𝒏 moles it becomes

𝑷𝑽 = 𝒏𝑹𝑻 (2–6)

Equation (2-6) is known as the general ideal gas law, and because it relates the specific
conditions or state, that is, the pressure, volume, and temperature of a given mass of gas,
it is called the equation of state of an ideal gas.

Real gases do not interact without energy exchange, and therefore do not follow the laws
of Boyle and of Gay-Lussac and Charles as ideal gases are assumed to do. To obtain a
numerical value for 𝑹

If 1 mole of an ideal gas is chosen, its volume under standard conditions of temperature
and pressure (i.e., :0°C and 760 mm Hg) has been found by experiment to be 22.414 liters.
Substituting this value in equation (2-6), we obtain

1 atm × 22.414 liters = 1 mole × R × 273.16 K

R = 0.08205 liter 𝒂𝒕𝒎⁄𝒎𝒐𝒍𝒆 K

3
The molar gas constant can also be given in energy units by expressing the pressure in
dynes/𝑐𝑚2(1 atm = 1.0133 x 10° dynes/cm²) and the volume in the corresponding units
of cm° (22.414 liters = 22,414 𝒄𝒎𝟐 ). Then

𝑷𝑽 (𝟏.𝟎𝟏𝟑𝟑 × 𝟏𝟎𝟔 ) ×𝟐𝟐.𝟒𝟏𝟒

R= =
𝑻 𝟐𝟕𝟑.𝟏𝟔

= 𝟖. 𝟑𝟏𝟒 × 𝟏𝟎𝟔 𝒆𝒓𝒈⁄𝒎𝒐𝒍𝒆 K

or, because 𝟏 𝒋𝒐𝒖𝒍𝒆 = 𝟏𝟎𝟕 𝒆𝒓𝒈𝒔,

R = 𝟖. 𝟑𝟏𝟒 𝒋𝒐𝒖𝒍𝒆𝒔⁄𝒎𝒐𝒍𝒆 K

The constant can also be expressed in 𝑐𝑎𝑙⁄𝑚𝑜𝑙𝑒 𝑑𝑎𝑔, employing 1 𝑐𝑎𝑙 = 4.184 𝑗𝑜𝑢𝑙𝑒𝑠
𝟖.𝟑𝟏𝟒 𝒋𝒐𝒖𝒍𝒆⁄𝒎𝒐𝒍𝒆 𝒅𝒆𝒈
R= = 𝟏. 𝟗𝟖𝟕 𝒄𝒂𝒍⁄𝒎𝒐𝒍𝒆 𝒅𝒆𝒈
𝟒.𝟏𝟖𝟒 𝒋𝒐𝒖𝒍𝒆𝒔⁄𝒄𝒂𝒍

Example 2-2
Calculation of Volume Using the Ideal Gas Law What is the volume of 2 moles of an ideal
gas at 25°C and 780 mm Hg?

Answer//
( 𝟕𝟖𝟎 𝐦𝐦⁄𝟕𝟔𝟎 𝐦𝐦 𝐚𝐭𝐦−𝟏 ) × 𝐕
= 𝟐 𝐦𝐨𝐥𝐞𝐬 × ( 𝟎. 𝟎𝟖𝟐𝟎𝟓 𝐥𝐢𝐭𝐞𝐫 𝐚𝐭𝐦⁄𝐦𝐨𝐥𝐞 𝐝𝐞𝐠) × 𝟐𝟗𝟖 𝑲
𝐕 = 𝟒𝟕. 𝟔𝟓 𝐥𝐢𝐭𝐞𝐫
Molecular Weight
The approximate molecular weight of a gas can be determined by use of the ideal gas law.
The number of moles of gas 𝒏 is replaced by its equivalent 𝐠⁄𝑴in which 𝐠 is the number
of grams of gas and 𝑴 is the molecular weight:
𝐠
𝑷𝑽 = 𝑹𝑻 (2 – 7)
𝐌
g𝑅𝑇
or 𝑀= (2 – 8)
𝑃𝑉

4
Example 2-3
Molecular Weight Determination by the Ideal Gas Law

If 0.30 g of ethyl alcohol in the vapor state occupies 200 mL at a pressure of 1 atm and a
temperature of 100°C, what is the molecular weight of ethyl alcohol? Assume that the
vapor behaves as an ideal gas. Write

Answer//
𝟎. 𝟑𝟎 × 𝟎. 𝟎𝟖𝟐 × 𝟑𝟕𝟑
𝐌=
𝟏 × 𝟎. 𝟐
𝐌 = 𝟒𝟔 𝐠⁄𝐦𝐨𝐥𝐞

Kinetic Molecular Theory

some of the more important statements of the theory:

1/ Gases are composed of particles called atoms or molecules, the total volume of which
is so small as to be negligible This condition is approximated in actual gases only at low
pressures and high temperatures.

2/ The particles of the gas do not attract one another; this statement applies only at low
pressures.

3/ The particles exhibit continuous random motion owing to their kinetic energy. The
average kinetic energy. E. is directive proportional to the absolute temperature of the gas.
or𝐸 = (3/2 )R T.

4/The molecules exhibit perfect elasticity; that is, there is no net loss of speed or transfer
of energy after they collide with one another and with the molecules in the walls of the
confining vessel, which latter effect accounts for the gas pressure.

5
From these and other postulates, the following fundamental kinetic equation is derived:
𝟏
𝑷𝑽= 𝒏𝒎𝒄𝟐 (2 – 9)
𝟑

where 𝑷 is the pressure and 𝑽 the volume occupied by any number 𝒏 of molecules of
mass 𝒎 having an average velocity [ 𝑪 with bar above ].
𝟑𝑹𝑽
𝝁=√ (2 – 10)
𝒏𝒎

Restricting this case to 1 mole of gas, we find that 𝑷 𝑽 becomes equal to 𝑹 𝑻 from the
equation of state (2-5), 𝒏 becomes Avogadro's number 𝑵𝑨 , and 𝑵𝑨 multiplied by the
mass of one molecule becomes the molecular weight 𝑴.

The root mean square velocity is therefore given by

𝟑𝑹𝑻
𝝁=√ (2 – 11)
𝑴

Example 2-4
Calculation of Root Mean Square Velocity What is the root mean square velocity of
oxygen (molecular weight, 32.0) at 25°C (298 K)?

Answer//
𝟑 ×𝟖.𝟑𝟏𝟒 × 𝟏𝟎𝟕 ×𝟐𝟗𝟖
𝛍=√ = 𝟒. 𝟖𝟐 × 𝟏𝟎𝟒 𝐜𝐦⁄𝐬𝐞𝐜
𝟑𝟐

Because the term 𝑛𝑚⁄𝑉 is equal to density, we can write equation (2-10) as
𝟑𝑷
𝝁=√ (2 – 12)
𝒅

Remembering ◊

that density is defined as a mass per unit volume, we see that the rate of diffusion of a
gas is inversely proportional to the square root of its density.

6
The van der Waals Equation for Real Gases
The fundamental kinetic equation (2-9) is found to compare with the ideal gas equation
because the kinetic theory is based on the assumptions of the ideal state. However, real
gases are not composed of infinitely small and perfectly elastic nonattracting spheres.
They are composed of molecules of a finite volume that tend to attract one another.

A number of such expressions have been suggested, the van der Waals equation being
the best known of these. For 1 mole of gas, the van der Waals equation is written as

𝒂
(𝑷+ ) (𝑽−𝒃)= 𝑹𝑻 (2 – 13)
𝑽𝟐

For the more general case of moles of gas in a container of volume 𝑽,

equation (2-13) becomes:

𝒂𝒏𝟐
(𝑷+ ) ( 𝑽 − 𝒏𝒃 ) = 𝒏𝑹𝑻 (2 – 14)
𝑽𝟐

The term 𝒂⁄𝑽𝟐 accounts for the internal pressure per mole resulting from the
intermolecular forces of attraction between the molecules b accounts for the
incompressibility of the molecules. When the volume of a gas is large, the molecules are
well dispersed. Under these conditions, 𝒂⁄𝑽𝟐 and become insignificant with respect to
𝑷 and V ,respectively. Under these conditions, the van der Waals equation for 1 mole of
gas reduces to the ideal gas equation, 𝑷𝑽 = 𝑹𝑻.

7
Example 2-5
Application of the van der Waals Equation

A 0.193-mole sample of ether was confined in a 7.35-liter vessel at 295 K. Calculate the
pressure produced using (a) the ideal gas equation and (b) the van der Waals equation.
The van der Waals a value for ether is 17.38 liter atm/mole; the b value is 0.1344
liter/mole. To solve for pressure, the van der Waals equation can be rearranged as follows:

Answer//
𝒏𝑹𝑻 𝒂𝒏𝟐
𝑷= −
𝑽−𝒏𝒃 𝑽𝟐

𝟎.𝟏𝟗𝟑 𝐦𝐨𝐥𝐞 ×𝟎.𝟎𝟖𝟐𝟏 𝐥𝐢𝐭𝐞𝐫 𝐚𝐭𝐦⁄𝐝𝐞𝐠 𝐦𝐨𝐥𝐞 ×𝟐𝟗𝟓 𝐝𝐞𝐠

a) 𝐏=
𝟕.𝟑𝟓 𝐥𝐢𝐭𝐞𝐫

= 0.636 𝑎𝑡𝑚

b)
(𝟎.𝟏𝟗𝟑 𝐦𝐨𝐥𝐞 ×𝟎.𝟎𝟖𝟐𝟏 𝐥𝐢𝐭𝐞𝐫 𝐚𝐭𝐦⁄𝐝𝐞𝐠 𝐦𝐨𝐥𝐞 ×𝟐𝟗𝟓 𝐝𝐞𝐠 𝟏𝟕.𝟑𝟖 𝐥𝐢𝐭𝐞𝐫𝟐 𝐚𝐭𝐦⁄𝐦𝐨𝐥𝐞𝟐 (𝟎.𝟏𝟗𝟑 𝐦𝐨𝐥𝐞 )𝟐
𝐏= −
𝟕.𝟑𝟓 𝐥𝐢𝐭𝐞𝐫 − (𝟎.𝟏𝟗𝟑 𝐦𝐨𝐥𝐞 )×( 𝟎.𝟏𝟑𝟒𝟒 𝐥𝐢𝐭𝐞𝐫⁄𝐦𝐨𝐥𝐞 ) (𝟕.𝟑𝟓 𝐥𝐢𝐭𝐞𝐫)𝟐

= 𝟎. 𝟔𝟐𝟔 𝒂𝒕𝒎

8
Example 2-6
Calculation of the van der Waals Constants

Calculate the pressure of 0.5 mole of 𝐶𝑂2 gas in a fire extinguisher of 1-liter capacity
at 27°C using the ideal gas equation and the van der Waals equation. The van der Waals
constants can be calculated from the critical temperature 𝑇𝐶 and the critical pressure 𝑃𝐶
(see the section Liquefaction of Gases for definitions):

Answer//
𝟐𝟕 𝑹𝟐 𝑻𝟐𝑪 𝑹𝑻𝑪
𝒂= and 𝒃=
𝟔𝟒𝑷𝑪 𝟖𝑷𝑪

The critical temperature and critical pressure of 𝐶𝑂2 are 31.0°C and 72.9 atm,
respectively. Using the ideal gas equation, we obtain
𝑛𝑅𝑇 0.5 𝑚𝑜𝑙𝑒 × 0.0821 𝑙𝑖𝑡𝑒𝑟 𝑎𝑡𝑚⁄deg 𝑚𝑜𝑙𝑒 × 300.15 𝑑𝑒𝑔
𝑃= =
𝑉 1 𝑙𝑖𝑡𝑒𝑟
= 12.32 𝑎𝑡𝑚

Using the van der Waals equation, we obtain

𝟐
𝟐𝟕 × (𝟎. 𝟎𝟖𝟐𝟏 𝒍𝒊𝒕𝒆𝒓 𝒂𝒕𝒎⁄𝐝𝐞𝐠 𝒎𝒐𝒍𝒆) × (𝟑𝟎𝟒. 𝟏𝟓 𝐝𝐞𝐠)𝟐
𝒂= = 𝟑. 𝟔𝟎𝟖 𝒍𝒊𝒕𝒆𝒓𝟐 𝒂𝒕𝒎⁄𝒎𝒐𝒍𝒆𝟐
𝟔𝟒 × 𝟕𝟐. 𝟗 𝒂𝒕𝒎

(𝟎.𝟎𝟖𝟐𝟏 𝒍𝒊𝒕𝒆𝒓 𝒂𝒕𝒎⁄𝒅𝒆𝒈 𝒎𝒐𝒍𝒆)×𝟑𝟎𝟒.𝟏𝟓 𝒅𝒆𝒈

𝒃= = 𝟎. 𝟎𝟒𝟐𝟖 𝒍𝒊𝒕𝒆𝒓⁄𝒎𝒐𝒍𝒆
𝟖×𝟕𝟐.𝟗 𝒂𝒕𝒎

𝒏𝑹𝑻 𝒂𝒏𝟐
𝑷= -
𝑽−𝒏𝒃 𝑽𝟐
(𝟎. 𝟓 𝒎𝒐𝒍𝒆 × 𝟎. 𝟖𝟐𝟏 𝒍𝒊𝒕𝒆𝒓 𝒂𝒕𝒎⁄𝒅𝒆𝒈 𝒎𝒐𝒍𝒆) × 𝟑𝟎𝟎. 𝟏𝟓 𝒅𝒆𝒈 𝟗𝟑. 𝟔𝟎𝟖 𝒍𝒊𝒕𝒆𝒓𝟐 𝒂𝒕𝒎⁄𝒎𝒐𝒍𝒆𝟐
= −
𝟏 𝒍𝒊𝒕𝒆𝒓 − (𝟎. 𝟓 𝒎𝒐𝒍𝒆 × 𝟎. 𝟎𝟒𝟐𝟖𝟖𝟐𝟏 𝒍𝒊𝒕𝒆𝒓⁄𝒎𝒐𝒍𝒆) (𝟏 𝒍𝒊𝒕𝒆𝒓)𝟐

= 𝟏𝟏. 𝟔𝟗 𝒂𝒕𝒎