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# a) Equation of state: Ideal gas equation of state, deviation of Real gas from ideal gas, van der waals

equation of state, correction for the intermolecular attractions, correction for finite size of molecules, evaluation of constants a and b, virial expansions, limitations of the van der Walls equation, Reduced coordinates, compressibility factor, the law of corresponding states as per van der Walls principle. b) Mixture of perfect gases: Mass Fraction, Mole fraction , Daltons Law of additive pressure, AmagatLeduc of additive volumes , Properties of mixture of ideal non reactive gases gas constant, molecular weight, specific heat, internal energy, enthalpy and entropy.

## Why do real gases deviate from the ideal behaviour ?

Real gases do not obey ideal gas equation under all conditions. They nearly obey ideal gas equation at higher temperatures and very low pressures. However they show deviations from ideality at low temperatures and high pressures. The deviations from ideal gas behaviour can be illustrated as follows: The isotherms obtained by plotting pressure, P against volume, V for real gases do not coincide with that of ideal gas, as shown below.

It is clear from above graphs that the volume of real gas is more than or less than expected in certain cases. The deviation from ideal gas behaviour can also be expressed by compressibility factor, Z. Compressibility factor (Z): The ratio of PV to nRT is known as compressibility factor. (or) The ratio of volume of real gas, Vreal to the ideal volume of that gas, V perfect calculated by ideal gas equation is known as compressibility factor.

## But from ideal gas equation: PVperfect = nRT or

Therefore

* For ideal or perfect gases, the compressibility factor, Z = 1. * But for real gases, Z 1.

Case-I : If Z>1 * Vreal > Videal * The repulsion forces become more significant than the attractive forces. * The gas cannot be compressed easily. * Usually the Z > 1 for so called permanent gases like He, H2.

Case-II: If Z < 1 * Vreal < Videal * The attractive forces are more significant than the repulsive forces. * The gas can be liquefied easily. * Usually the Z < 1 for gases like NH3, CO2, SO2.

The isotherms for one mole of different gases, plotted against the Z value and pressure, P at 0oC are shown below:

* For gases like He, H2 the Z value increases with increase in pressure (positive deviation). It is because, the repulsive forces become more significant and the attractive forces become less dominant. Hence these gases are difficult to be condensed. * For gases like CH4, CO2, NH3 etc., the Z value decreases initially (negative deviation) but increases at higher pressures. It is because: at low pressures, the attraction forces are more dominant over the repulsion forces, whereas at higher pressures the repulsion forces become significant as the molecules approach closer to each other. * But for all the gases, the Z value approaches one at very low pressures, indicating the ideal behaviour. Also consider the following graphs of Z vs P for a particular gas, N2 at different temperatures.

In above graphs, the curves are approaching the horizontal line with increase in the temperature i.e., the gases approach ideal behaviour at higher temperatures.

Real gases deviate from the ideal gas behavior because at low temperature gas molecules have less kinetic energy which makes them not to attract. The gases that deviate from the ideal gas behavior are referred to as non-ideal gases.

## Derivation of PV=nRT, The Equation of Ideal Gas

According to the kinetic theory of gas, - Gases are composed of very small molecules and their number of molecules is very large. - These molecules are elastic. - They are negligible size compare to their container. - Their thermal motions are random. To begin, let's visualize a rectangular box with length L, areas of ends A1 and A2. There is a single molecule with speed vx traveling left and right to the end of the box by colliding with the end walls.

## 3D Demonstration of Ideal Gas

The time between collisions with the wall is the distance of travel between wall collisions divided by the speed.

## 2. According to Newton, force is the time rate of change of the momentum

3. The momentum change is equal to the momentum after collision minus the momentum before collision. Since we consider the momentum after collision to be mv, the momentum before collision should be in opposite direction and therefore equal to -mv. 4. According to equation #3, force is the change in momentum get an equation of average force momemtum in term of particle velocity from equation #2. multiply by the frequency divided by change in time , we take change in . To

5. The pressure, P, exerted by a single molecule is the average force per unit area, A. Also V=AL which is the volume of the rectangular box.

6. Let's say that we have N molecules of gas traveling on the x-axis. The pressure will be

7. To simplify the situation we will take the mean square speed of N number of molecules instead of summing up individual molecules. Therefore, equation #7 will become

8. Earlier we are trying to simplify the situation by only considering that a molecule with mass m is traveling on the x axis. However, the real world is much more complicated than that. To make a more accurate derivation we need to account all 3 possible components of the particle's speed, vx, vy and vz. 9. Since there are a large number of molecules we can assume that there are equal numbers of molecules moving in each of co-ordinate directions. 10. Because the molecules are free too move in three dimensions, they will hit the walls in one of the three dimensions one third as often. Our final pressure equation becomes

11. However to simplify the equation further, we define the temperature, T, as a measure of thermal motion of gas particles because temperature is much easier to measure than the speed of the particle. The only energy involve in this model is kinetic energy and this kinetic enery is proportional to the temperature T.

12. To combine the equation #11 and #12 we solve kinetic energy equation #12 for mv2. 13. Since the temperature can be obtained easily with simple daily measurement like a thermometer, we will now replace the result of kinetic equation #13 with with a constant R times the temperature, T. Again, since T is proportional to the kinentic energy it is logical to say that T times k is equal to the kinetic energy E. k, however, will currently remains unknown.

## 14. Combining equation #14 with #11, we get:

15. Because a molecule is too small and therefore impractical we will take the number of molecules, N and divide it by the Avogadro's number, NA= 6.0221 x 1023/mol to get n (the number of moles) 16. Since N is divided by Na, k must be multiply by Na to preserve the original equation. Therefore, the constant R is created. 17. Now we can achieve the final equation by replacing N (number of melecules) with n (number of moles) and k with R.

## 17. Calculation of R & k

According to numerous tests and observations, one mole of gas is a 22.4 liter vessel at 273K exerts a pressure of 1.00 atmosphere (atm). From the ideal gas equation above:

A. B. C.