Ideal Gas Equation

By combining Boyle's and Charles' laws, an equation can be derived that gives the simultaneous effect of the changes of pressure and temperature on the volume of the gas. This is known as combined Ideal Gas Equation. A simple and direct method of deriving this equation is as follows: According to Boyle's law, for a given mass of a gas at constant temperature

According to Charles' law,

Combining (i) and (ii)

or

or

Now, if V1 is the volume of a gas at temperature T1 and pressure P1. V2 is the volume of same amount of gas at temperature T2 and pressure P2, then

The above relationship is very useful for converting the volume of a gas from one set of conditions to another. The numerical value of the constant of proportionality (K) depends upon the quantity of gas. The volume of a gas is directly proportional to the number of moles of gas at constant temperature and pressure (Avogadro's law). This means that 'K' is directly proportional to the number of moles, 'n', i.e., K n

or K = nR, where 'R' is the universal gas constant of proportionality. The value of 'R' is same for all gases. However, the numerical value of 'R' varies with the units in which pressure and volume are expressed. Therefore the Ideal gas Equation is derived as:

For one mole (n = 1), PV = RT (Ideal Gas Equation) The Ideal Gas Equation is also known as the equation of state for gases as it expresses the quantitative relation ship between the four variables that describe the state of the gas. The word 'ideal' is used here because in reality no gas obeys the above condition and the gases, which deviate from ideality are called as real gases.

Universal gas constant (R)

From the above ideal gas equation:

The universal gas constant is a measure of energy change (work done) per mole of the gas for one degree change in its temperature.

Numerical Value of R
The magnitude and unit of 'R' depends upon the units in which pressure, volume and temperature are expressed.

Conditions and problems I)When pressure is expressed in atmosphere and volume in litres
Under standard condition of temperature and pressure i.e., when P = 1 atm T = 273.15 K V = 22.414 L mol This gives,
-1

II
) When pressure is expressed in atmosphere, and volume in mL Here, P = 1 atm T = 273.15 K V = 22414 mL mol This gives,
-1

III) R in energy units

When,

If 'R' is to be expressed in CGS units, the unit of pressure should be dyne cm and volume in cm mol . Then, Normal temperature T = 273.15 K Normal pressure, P = (1 x 76 x 13.6 x 981) dyne cm
-2

-2

-1

Molar volume under normal temperature and pressure = 22414 cm mol Therefore,
3 -1

= 8.314 x 10 erg deg mol

7

-1

-1

Since, 4.182 x 10 erg = 1calorie Hence,

IV) In SI units
In the SI system of units, under NTP conditions, P = 101325 N m T = 273.15 K V = 22.414x10 m Therefore,
-3 3 -2

= 8.314 J mol K

-1

-1

The value of Gas constant R in different units

Problems
5. Calculate the number of moles of hydrogen (H2) present in a 500 cm sample of hydrogen gas at a pressure of 760 mm of Hg and 27C.
3

Solution
According to ideal gas equation, PV = nRT

T = 27 + 273 = 300 K, R=82.1 cm atm K mol

-1

-1

n = 0.0203 mol = 2.03 x 10 mol. 6. About 200 cm of a gas is confined in a vessel at 20C and 740 mm Hg pressure. How much volume will it occupy at S.T.P.?
3

-2

Solution
We are given P1 = 740 mm Hg P2 = 760 mm Hg T1 = 20 + 273 = 293K T2 = 273 K V1 = 200 cm V2 = ? According to gas equation,
3

Substituting the values, we get

= 181.4 cm . 7. Calculate the volume occupied by 2 moles of an ideal gas at 2.5 x 10 Nm pressure and 300 K temperature.
5 -2

Solution
According to ideal gas equation,

n = 2 mol, T = 300 K, P = 2.50 x 10 Nm R = 8.314 Nm K mol

-1 -1

-2

= 19.95 x 10 m =19.95dm

-3

Gas Laws - Boyle's Law

The study of behaviour of gases has led to the formulation of a few important generalisations called as Gas Laws.

Boyle's Law
Robert Boyle proposed this law in the year 1662, giving the relationship between pressure and volume of given mass of a gas at constant temperature. This law states that volume (V) of a given mass of gas is inversely proportional to the pressure (P) at constant temperature. Mathematically it can be expressed as,

or PV = k = constant At a given temperature, when the pressure of the gas is changed from P1 to P2 the relation becomes P1 V1 = P2 V2 = constant where, V2 is the new volume of the gas. The product of volume and pressure for a given mass of a gas at constant temperature is constant. This aspect can be experimentally verified by taking the pressure volume data for a gas like 10g of oxygen at 25 C. It is observed that with the increase in pressure the volume decreases and the product 'PV' remains constant. This data when plotted with 'P' along the x-axis and 'V' long the y-axis gives a curve.
o

Fig: 2.2 - Variation of P and V at constant T The curve shows the inverse relation of 'P' and 'V'. When the pressure is P 1, the volume is V1 and when the pressure is increased to P2, the volume V2 is smaller than V1. If the graph is plotted between 'P' and 1 / V, a straight line passing through the origin is obtained. On plotting the product 'PV' along y-axis and Pressure 'P' along x-axis, a horizontal line is obtained, indicating 'PV' to be constant even if we change pressure.

Fig: 2.3 - Plot of P versus 1/V The P-V curve for a given gas is different at different temperatures. The plot of 'PV' against 'P' at different temperature is known as Isotherms. The higher curve corresponds to higher temperature. Boyle's law expresses the compressible nature of gas, which gives a measure of its increased density.

Problem
1. A gas occupies a volume of 250 mL at 745 mm Hg and 25 C. What additional pressure is required to reduce the gas volume to 200mL at the same concentration?
o

Solution
P1 = 745 mm Hg V1 = 250 mL P2 = ? V2 = 200mL P1V1 = P2V2

The additional pressure required is 931.25 - 745 = 186.25 mm.

Graham's Law of Diffusion

Gases have the tendency to spontaneously intermix and form a homogenous mixture without the help of external agency. This is due to the presence of large amount of empty space between the gas molecules that makes their movement rapid into each other. The gases move from a region of higher concentration to a region of lower concentration until the mixture attains uniform concentration. Graham studied the rate of diffusion of various gases and gave this law. It states that under similar conditions of temperature and pressure, the rates of diffusion of gases are inversely proportional to the square roots of their densities.

If r1 and r2 are the rates of diffusion of two gases 'A' and 'B' and r1 and r2 are their densities, then

Molecular mass is twice the vapour density, substituting this in the above equation, we have

where M1 and M2 are the molecular masses of the two gases. Thus, the rate of diffusion of gases are inversely proportional to the square root of their molecular masses. Rate of diffusion is also equal to the volume of the gas, which diffused per unit time,

If V1 and V2 are the volumes of the gases diffusing in time t1 and t2 respectively, then

Therefore,

If the volume diffused is the same, (V1 = V2) Then,

Graham's law is useful in:

Separation of gases having different densities by diffusion. Determining the densities and molecular masses of unknown gases by comparing their rates of diffusion with known gases.

Separating the isotopes of some of the elements.

Effusion
When the gases contained in a vessel are allowed to escape through a small aperature, it is effusion.

Fig: 2.6 - Process of diffusion and effusion

Problem
4. An unknown gas diffuses four times as quickly as oxygen. Calculate the molecular mass of the gas.

Solution
Let the rate of diffusion of oxygen be r(O2) = r1 The rate of diffusion of the unknown gas r (x) = 4r

Molecular mass of O, M(O) = 32 Molecular mass of unknown gas M (x) = M From Graham's Law of diffusion,

or

Squaring on both sides,

Charles' Law
Charles formulated this law in 1787 giving the relationship between volume and temperature of a gas. This law stated that at constant pressure, the volume of a given mass of gas increases or decreases by 1/273 of its volume at 0 C for every one degree rise or fall.
o

or

A plot of volume along x-axis and temperature along y-axis gives a straight line intercepting the y-axis. When this line is extrapolated to lower temperature, it cuts the x-axis, which represents the zero volume.

Fig: 2.4 - Plot of volume versus temperature (P constant) The temperature at which the volume of the gas becomes zero is found to be -273 C, which is independent of the nature and pressure of the gas. The lowest temperature below which volume does not exist (negative), is called the absolute zero. Temperature measurements based on the absolute zero is known as absolute scale of temperature or Kelvin temperature scale. Charles' law is mathematically represented as:
o

273 + t = T (K) and 273 =T0 which corresponds to 0 C on absolute temperature scale

Thus, V/T constant = k'

The volume of a given mass of a gas is directly proportional to the absolute temperature at constant pressure. If V 1 is the volume of a certain mass of gas at temperature T1 and V2 is the volume of the same mass of the same gas at temperature T2 at constant pressure, then,

The validity of Charles' law can be determined by measuring the volumes of a given mass of a gas at different temperatures, at constant pressure. The value of V/T remains to be constant in this study. The curves obtained by plotting volume temperature ratio against different pressures are called isobars. Charles described the expansive nature of gases with lower density.

Problem
2. A sample of helium has a volume of 520 cm at 100 C. Calculate the temperature at which the volume will become 26cm . Assume that pressure is constant?
3 3 o

Solution V1 = 520 cm3 V2 = 260 cm3

T1 = 100 + 273 = 373K T2 = ?

or

T2 = 186.5 K t = 186.5 - 273 = 86.5 C.

o

Dalton's Law of Partial Pressures

Dalton proposed this law on the pressure exerted by a mixture of non-reacting gases in an enclosed vessel. The law of partial pressure states that the total pressure exerted by a mixture of two or more non-reacting gases in a definite volume is equal to the sum of the individual pressures, which each gas would exert if it occupies the same volume at a constant temperature. If p1, p2, p3 are the individual partial pressures of the known gases, then the total pressure 'P' of the mixture of gases at the same temperature and pressure is given by the relation: P = p1 + p2 + p3 + . Partial pressure is the pressure exerted by the gas if present alone in the vessel at the same conditions of temperature. For example, A gas 'A' having a pressure of 300 mm Hg is contained in a vessel and another gas 'B' with a pressure of 400 mm Hg is contained in another vessel, are mixed in the third vessel at the same temperature. The total pressure in the third vessel is, P = PA + PB = 300 + 400 = 700 mm Hg

Fig: 2.5 - Dalton's law of partial pressures Dalton's law is used to calculate the pressure of a gas.

Problem
3. A 10 L flask at 298 K contains a gaseous mixture of CO and CO 2 at a total pressure of 1520 mm of Hg. If 0.20 mole of CO is present, find the partial pressure of CO and that of CO2?

Solution
According to Dalton's Law: pCO + pCO2 = P = 1520 mm of Hg

= 0.49 atm. Partial pressure of CO2, pCO2= P - (pCO) = 2.0 - 0.49 = 1147.6 mm of Hg

Kinetic Molecular Theory of Gases

In order to explain the observed behaviour of gases, a model was proposed based on the molecular and kinetic concept of gas molecules. This model takes into account the particulate nature of matter and the constant movement of particles.

Postulates of Kinetic Theory

All gases are made up of large number of minute particles called molecules.

Large distances separate the molecules so that the actual volume of the molecules is negligible as compared to the total volume of the gas.

The molecules are in a state of constant rapid motion in all directions, colliding with one another and also with the walls of the container.

The molecular collisions are perfectly elastic with no loss of energy and only redistribution of energy during collision.

There are no attractive or repulsive forces between the molecules. The pressure exerted by the gas is due to the bombardment of its molecules on the walls of the container per unit area.

The average kinetic energy of the gas molecules is directly proportional to the absolute temperature.

On the basis of these postulates an equation for the pressure of the gas is derived as

This is called the Kinetic gas equation where 'N' is the number of molecules in volume 'V', 'm' is the mass of the

Liquefaction of Gases
There are large empty spaces (voids) separating the tiny molecules of gases from one another. Each molecule enjoys an almost independent existence. Molecules are in a state of continuous rapid motion and have negligible attractive forces between them due to wide separation. This is particularly so, when temperature is high and pressure is low. When the temperature of the gas is lowered, both the volume of the gas and the kinetic energy of the molecules decrease. The molecular motion becomes slow and molecules become sluggish. The progressive decrease of temperature brings the molecules closer and closer because they are unable to resist the attractive force that starts operating between them. Ultimately, at sufficiently low temperature, the voids between the molecules become less than 10 cm and the gas changes into liquid state. This process of liquefaction by bringing gas molecules closer can also be achieved by increasing the pressure of the gas: this also decreases the volume of the gas. For example, sulphur dioxide can be liquefied at 265 K if pressure is 760 mm of Hg. It can also be liquefied at 293K if the pressure is increased to 2470 mm of Hg. Thus, liquefaction of gases can be achieved by either decrease of temperature or by increase of pressure.
-5

Concept of critical temperature

Experimental observations have shown that effect of temperature is more significant in achieving liquefaction than that of pressure. This is due to the fact that for every gas there is a certain temperature above which it cannot be

liquefied how so ever high the pressure may be. The kinetic energy of gas molecules above this temperature is sufficient enough to overcome the attractive forces. This temperature is referred to as the critical temperature of the gas. It may be defined as the temperature above which a gas cannot be liquefied by application of pressure. A gas will remain as gas above critical temperature and in order to liquefy it by compression, it has to be cooled to its critical temperature. Critical temperature is denoted by Tc. For example, Tc of CO2 = 304.1 K.

Critical pressure (P
c)

The pressure required to liquefy the gas at its critical temperature is called critical pressure. For example, the value of Pc for CO2 = 55328 mm of Hg.

Critical volume (Vc)

The volume of one mole of the gas at critical temperature and critical pressure is called critical volume. For example, value of Vc for CO2 = 94.0 cm mol
3 -1

The parameters Tc, Pc and Vc for a gas are collectively called 'critical constants'.

Ideal and Real Gases

An ideal gas is one, which obeys the general gas equation of PV = nRT and other gas laws at all temperatures and pressures. A real gas, does not obey the general gas equation and other gas laws at all conditions of temperature and pressure.

Effect of pressure
All gases are known to exist as real gases and show ideal behaviour only to some extent under certain conditions. When PV = nRT for ideal gases, then the ratio

For real gases Z may be less or more than one. If Z<1 then it is called negative deviation which means that the gas more compressible. if z>1 then the gas is less compressible and it is called positive deviation. It is observed that the deviations are low at low pressures. At high pressures the deviations depends on the nature of the gas.

A plot of

versus P for some common gases are shown in the figure.

Fig: 2.7 - Plot of compressibility factor as a function of P For H2 and He, 'Z' is greater than one while for N2, CH4 and CO2 'Z' is lesser than one. This means that these gases are more compressible at low pressures and less compressible at high pressures than expected from ideal behaviour.

Effect of temperature
The effect of temperature on the behaviour of real gases is studied by plotting the value of 'PV' against temperature. It is observed that the deviations from ideal behaviour is less with the increase in temperature. Thus, real gases show ideal behaviour at low pressures and high temperatures.

Causes for deviations

In order to know the causes for deviations from ideality, Van der Waal pointed out the faulty assumption that were made in formulating the kinetic molecular model of gases.

The assumption that the volume occupied by the molecular mass is negligible as compared to the total volume of the gas is invalid. Although this volume is 0.1% volume of the total volume of the gas, the volume of the molecules of gas remain same as compared to the decrease in the total volume of the gas. The decrease in volume occurs with the decrease in temperature and increase in pressure, but the volume of the molecules cannot be neglected.

The forces of attraction between the gas molecules were considered to be negligible. This assumption is only valid at low pressures and high temperatures because in these conditions the molecules lie far apart. But at high pressures and low temperatures the volume of the gas is small and so the attractive forces though very small, exist between them.

Hence, Van der Waal who incorporated the idea of finite molecular volume and intermolecular forces modified the Ideal Gas Equation as follows:

Volume correction was made stating that the free volume of the gas is actually less than the observed volume. A suitable volume term 'b' is subtracted from the observed volume known as the excluded volume or

correct volume. The correction term, 'b' is a constant depending upon the nature of the gas. For 'n' moles of gas, the correction term is 'nb' and so the corrected volume is given by, Vcorrected = (V-nb) for 'n' moles. Correction due to intermolecular forces is considered in terms of the pressure. A molecule at the wall of the container experiences an inward pull due to attractive intermolecular force of the neighbours. The molecules strike the wall with a lesser force and so the observed pressure is less than the ideal pressure. The pressure correction term

Substituting these values for pressure and volume, the ideal gas equation can now be written as:

This equation is Van der Waal's equation of state. Here, the constant 'a' measures the forces of attraction between the molecules of the gas and 'b' relates to the incompressible volume of the molecules, measuring the size of the gas molecules. One can now summarize the differences between ideal and real gases as follows:

Difference between Ideal and Real Gases

Introduction to difference between ideal and real gases: Gases that obey the gas laws at all conditions of temperature and pressure is termed as ideal gases. Real gases have definite volumes and are attracted to one another. Real gases do not obey the gas laws at all standard temperature and pressure conditions and deviate from their ideal behaviour when the gases become voluminous and massive due to attractions between each other.

Differences between Ideal Gases and Real Gases:

Let us look into how the ideal gases differ from real gases. Ideal gases allows the assumption of the ideal gas law that the quantities that are measured such as pressure, temperature, volume and the number of particles are in exact proportions in gases. Ideal gas law may be represented by PV=nRT. Real gases deviate from the ideal behaviour when the gas particles become massive and voluminous because of the attractions which may be utilized for simulating the behaviour of real gas by the Vanderwaals equation which is p + ((n2a)/V2)(V - nb) = nRT. The constants a and b in the law are a derivative of the agreement between the equation and the behaviour observed. The constant a denotes the forces of attraction between the molecules and the constant b stands for the volume constant.

The Differences between Ideal Gases and Real Gases are Mentioned in a Tabular Form Below
Real gases Real gases does not obey gas laws at all standard temperature and pressure Ideal gases Ideal gases obey gas laws at all ideal temperature and pressure

Real gases follows Vanderwaals equation: p + ((n2a)/V2)(V - nb) = nRT Has volume, mass, velocity Has electronic interactions Real gases condenses, has a triple point and sublimes Real gases liquefy when cooled to their boiling point Interacts with others

Ideal gases obey ideal gas law PV=nRT Has no volume but has mass and velocity Does not have potential electronic interaction Do not condense and has no triple point Can be compressed or cooled infinitely and does not liquefy Totally independent of others

Conclusion for Differences between Ideal Gases and Real Gases:

It is assumed that gases exhibit the ideal gas behaviour that involves the property of gas compression, liquefaction and gases have a definite volume

Behaviour of Real Gases: Deviation from Ideal Gas Behaviour

BEHAVIOUR OF IDEAL GASES

Gases do not have definite shape or volume. In case of gases The distance between the molecules is very large. The force of attraction between the molecules is negligible. Molecules of gas move in straight lines And occupy the whole space available in a container. Impact of gas molecules with high velocity on the walls of the container causes the pressure to be exerted on the walls. On an average the same number of molecules strike a given area on the wall in unit time, hence the pressure is equal, uniform and exert in all directions. Gases have low density. Gas molecules have the tendency to mix with other gases. Temperature of a gas is the average kinetic energy possessed by a molecule. Kinetic energy increases with increase in temperature.

Pressure of a gas is the average force exerted by the bombardment of gas molecules on the walls of a container per unit area of the container. Volume of the gas Practically all gases liquefy or solidify before reaching this temperature. is the space occupied by the fixed mass of the gas. By keeping the temperature of a fixed mass of a gas constant, if the pressure is increased the volume correspondingly decreases. By keeping the temperature of a fixed mass of a gas constant if the pressure is increased the volume decreases.

Behaviour of Real Gases: Deviation from Ideal Gas Behaviour:the above Concept was Generalized by Robert Boyle
Boyles law temperature remaining constant the volume of a given mass of a gas is inversely proportional to its pressure. V is inversely proportional to 1/P V = K X 1/P

Charles law Pressure remaining constant, the volume of a given mass of a dry gas increases or decreases by 1/273 of its original volume at 0degree Celsius for each degree centigrade rise or fall in temperature. Consider a known mass of a gas of volume 273 cc. at temperature 0degree Celsius At -1degree Celsius the volume will be 272cc. At -2degree Celsius the volume will be 271cc At -273degree Celsius the volume will be zero. The temperature -273degree Celsius is called absolute zero. Reduction of volume of a gas to 0cc. is theoretical concept. practically all gases liquefy or solidify before reaching this temperature. Absolute scale of temperature The new temperature scale with its zero at -273degree Celsius and each degree equal to one degree on the Celsius scale is called Kelvin or absolute scale of temperature. Based on the above scale Charles states Pressure remaining constant the volume of a given mass of a gas is directly proportional to its absolute (Kelvin) temperature V is proportional to T Gas equation According to Boyles law at constant temperature V Is proportional to 1/ P Charles law V is proportional to T On combining these two laws V is proportional to T/P

V= K. T/P On rearranging the above equation PV/T = K P1V1/ T1 = P2V2/T2 This is the required gas equation.

Behaviour of Real Gases: Deviation from Ideal Gas Behaviour:some Laws:Gaylussacs Law It states that when gases react they do so in volumes which bear a simple whole number ratio to one another and to the volumes of the products, if gaseous, provided the temperature and pressure of the reacting gases and their products remain constant. Avogadros Law Equal volumes of all gases under the same conditions of temperature and pressure contain the same number of molecules. Grahams Law The rate at which the gas molecules diffuse is inversely proportional to the square root of its density. Daltons Law of partial pressure The pressure of a mixture of gases is the sum of the partial pressures of the individual components.