Module 1: Gaseous State `Maxwells distribution of molecular velocities (No derivation) average, most probable and rms velocities,

collision number and collision frequency, mean free path, deviation of gases from ideal behaviour Boyle temperature, derivation of vander waals constants and critical constants Law of corresponding states reduced equation of state, Joule Thomson effect, liquefaction of gases Lindes and claudes processes - 9 Hrs Maxwells distribution of molecular velocities Molecules of a gas are in constant rapid motion. During this random movement, they collide with each other and transfer energy from one molecule to another and thus change their velocities. Thus the different molecules in a gas will have different velocities and will be constantly changing. A fraction of molecules will have a same particular velocity and there is a broad distribution of velocities over different fraction of molecules. Maxwell calculated the distribution of velocities from the laws of probability and derived the following equation (called Maxwells law of distribution of molecular velocities) for the distribution of molecular velocities.

dNc= number of molecules having velocities between c and c+dc N= total number of molecules M=molar mass T=temperature on absolute scale R = molar gas constant dNc/N = fraction of the total number of molecules having velocities between c and c+dc Maxwell distribution curve Fraction of molecules are plotted against velocity possessed by gas molecules.

Fraction of molecules with too low or too high velocities is very small. The area under the curve gives the number of molecules The velocity possessed by most of the molecules is called most probable velocity ( ). The peak of the velocity distribution curve corresponds to . On increasing the temperature of a gas, the molecular motion increases and hence the most probable velocity increases. At higher temperature, the entire curve shifts towards right and become more broad. At higher temperature more molecules have high velocities and fewer have low velocities. Types of molecular velocities (i) Most probable velocity ( ) The velocity possessed by the maximum number of molecules of a gas at a particular temperature is called the most probable velocity. From Maxwell s distribution equation,

(ii)

Average velocity (v) The arithmetic mean of the different velocities possessed by the molecules of a gas at a given temperature is called the average velocity.

C1, c2 . Are the individual velocities of different molecules. n is the total number of molecules. From Maxwell s distribution equation,

(iii)

Root mean square (RMS) velocity (u) The square root of the mean of the squares of velocities of different molecules of a gas at a given temperature is called RMS velocity.

From kinetic theory of gases,

Since PV=RT and density d = M/V,

Relation between molecular velocities : v: u = 2 : 8/T : 3 = 1 : 1.128 : 1.224 = 0.816 : 0.921 : 1 Collision properties The molecules in a gas are constantly colliding with one another. Collision diameter(W)

It is the closest distance between the centers of the two molecules taking part in a collision. Whenever the distance between the centers of two molecules is less than W, there would occur a collision between them. Collision number (Z1) The number of collisions suffered by a single molecule per unit time per unit volume of a gas is known as collision number. From kinetic gas theory

W=collision diameter V=average velocity V= number density (number of molecules per unit volume of the gas) Collision Frequency (Z11) It is the number of collisions occurring per unit time per unit volume of a gas.

Mean free path (P) The mean distance travelled by a gas molecule between two successive collisions is called mean free path

Distance travelled by a molecule in one second = average velocity i.e., v = Z1 P therefore, P = v/z1 Or

Since PV=nRT and R =kNA (k-Boltzmann constant, NA Avogadro Number); PV = nNAkT = NkT (N- total number of molecules) P = NkT/V = VkT (since, V=N/V) OR, V = P/kT Hence,

Thus P is proportional to 1/P. That is at low pressure, P will be larger and this means that at low pressure the collision of molecules with the walls of the container will be greater since P gets value comparable to the container dimensions.

Deviation of gases from ideal behavior A gas which obeys the ideal gas equation, PV=nRT under all conditions of temperature and pressure is called an ideal gas. That is an ideal gas obeys all the gas laws at all temperatures and pressures. Real gases do not obey the ideal gas equation or gas laws under all conditions of temperature and pressure, but show marked deviation from ideal behavior.
At low pressures and high temperatures, the real gases obey the gas laws but at high pressures and low temperatures, real gases deviate from ideal behavior. Generally, larger deviations from ideal behavior are shown by those gases which are easily liquefiable such as CO2, SO2 and NH3. Deviation of real gases from ideal behavior can be represented in terms of compressibility factor, Z.

Fro an ideal gas, Z=1 under all conditions of temperature and pressure. Any deviation of Z from unity indicates the deviation from ideal behavior. A plot of Z against P is used to illustrate the non ideal behavior of gases.

Effect of pressure on Z At very low pressures (up to 10 atm.) , Z is approximately equal to unity for all gases. That is at low pressures real gases exhibit nearly ideal behavior. As the pressure is increased Z continuously increases for H2 and He (Z>1) and thus their curves lie above the ideal curve at all pressures. For N2 and CO2, Z first decreases (Z<1), passes through a minimum and then increases continuously (Z>1) with pressure. The dip is greater for easily liquefiable gases like CO2. Effect of Temperature The deviation from the ideal behavior becomes less and less with increase in temperature. The figure below shows the plot of Z versus P of N2 for various temperatures. At low temperature Z<1 and the dip in the curve is large. At a certain temperature the minimum in the curve vanishes and the curve remain horizontal for an appreciable range of pressure. At this temperature Z is almost unity and Boyle s law is obeyed for an appreciable range of pressure. This temperature, at which a gas obeys Boyle s over an appreciable range of temperature is called Boyle temperature. Boyle temperature of each gas is characteristic. Boyle temperature of N2 is 332K (590 C).

Below Boyle temperature PV first decreases, approaches an minimum and then increases. Above Boyle temperature, PV shows a continuous increase with increase in pressure. Thus in conclusion, at low pressure and high temperature, real gases show nearly ideal behavior. But at high pressures and low temperatures real gases deviates significantly from ideal behavior. Causes for the Deviation from ideal behavior- van de Waals equation Van der Waal attributed the deviation of real gases from ideal behavior to two wrong postulates of the kinetic theory. (i) (ii) The molecules in a gas are point masses and possess no volume There are no intermolecular attraction in a gas

Therefore the ideal gas equation PV=nRT derived from kinetic theory could not hold good for real gases. Van der Waal introduced two correction terms, one for the Pressure and the other for the Volume, in the gas equation in order to make it applicable to the real gases. Volume correction Volume of a gas is the free space in the container in which the molecules move about. For an ideal gas, volume is the same as the volume of the container, since the molecule itself are point masses and have zero volume and hence the entire space in the container is available for the free movement of molecules. In the case of real gases, van der Waal s assumed that the molecules are rigid spheres which possess a definite volume. The volume of the real gas is therefore volume of the container minus the actual volume possessed by the molecules themselves.

If b is the effective volume of the molecules of one mole of a gas, the volume of the real gas is given as, (V-b) For n moles of gas, the corrected volume is given as, V = nb b is termed excluded volume or co-volume, which is a constant and characteristic for each gas. It can be shown that the excluded volume is four times the actual volume of the molecules.

Consider two molecules colliding each other. It is evident that they cannot approach each other closer than a distance of 2r. where r is the radius of one molecule. Therefore the space indicated by the dotted sphere having radius 2r will not be available to all other molecules of the gas. That is this spherical space is excluded per pair of molecule. Excluded volume for two molecules = 4/3 T(2r)3 = 8 x 4/3 Tr3 = 8 Vm Excluded volume for one molecule = x 8 xVm = 4 Vm Where Vm is the actual volume of a gas of molecule. Therefore the excluded volume of the gas molecules is four times the actual volume of molecules. Pressure correction This correction is done by considering the attractive force between the gaseous molecules in real gases, which is considered as absent in ideal gases. A molecule in the interior of a gas is attracted by other molecules on all side and thus cancel out. But when a molecule is about to strike the wall of the container, it is attracted by molecules on one side only. Hence it experiences an inward pull and so it strikes the wall with a reduced velocity and the actual pressure of the gas, P, will be less than the deal pressure Pideal.. Consequently, it is necessary to add a correction term p to the observed pressure, in order to obtain the ideal pressure P = Pideal p Pideal. = P+p

p is determined by the force of attraction between the striking molecules and the molecules pulling them inward. The force and hence the pressure depends upon both the concentration of the molecules (number of moles per unit volume n/V) about to strike and the molecules pull them inward.

Thus, p n/V x n/V n2/V2

ie. p

p = a n2/V2 n is the number of moles and V is the volume of the gas thus the corrected pressure is

That is the ideal pressure for n moles of a real gas is P + an2/V2. Van der Waal s Equation Substituting the values of corrected pressure and volume in the ideal gas equation, PV = nRT, we have

This equation is called van der Waals equation for n moles of a gas. For one mole, the equation becomes,

The constants a and b are known as van der Waals constants. These are characteristic of each gas. Critical constants Gases can be liquefied by lowering the temperature and increasing the pressure. But for every gas there is a temperature below which only the gas can be liquefied. The temperature above which a gas cannot be liquefied whatever be the pressure applied is called Critical temperature, Tc. The minimum pressure required to liquefy a gas at its critical temperature is known as Critical Pressure, Pc of the gas. The volume occupied by one mole of a gas at its critical temperature and critical pressure is called critical volume, Vc. Tc, Pc and Vc of a gas are collectively called critical constants. All gases have characteristic critical constants.

At critical temperature and critical pressure a gas becomes identical with its liquid state and is said to be in the critical state. At critical temperature the phases intermix so well that it is impossible to distinguish between them. The gas and liquid have the same density and are indistinguishable.

The indistinguishable intermixing of the gaseous and liquid phases is known as continuity of state.This phenomenon is utilized in the experimental determination of critical constants of a gas.s
The smooth merging of the gas with its liquid is known as the critical phenomenon. Critical phenomena of CO2 The pressure-volume curve of a gas at constant temperature is called isotherm. For an ideal gas, at constant temperature, PV will be a constant and hence the isotherm would be a rectangular hyperbola. The isotherms of CO2 for a series of temperature are plotted by Andrews and are shown below. The critical temperature of CO2 is 31.1 0C. The three type of isotherms are (a) above 31.1 0C (b) below 31.1 and (c) one at 31.1 0C Isotherm above 31.1 0C These are rectangular hyperbolas and are similar to that of an ideal gas. Above 31.1 0C CO2 always exists in the gaseous state. There is no possibility for liquefaction of CO2 whatever be the pressure applied. Isotherms below 31.1 0C Here the isotherms have three parts. Curve AB along which volume decreases gradually with increase of pressure Horizontal portion BC along which liquefaction of gas occurs. At B liquefaction begins and at C liquefaction becomes complete. Vertical portion CD corresponds to liquid CO2 which is not compressible. Isotherm at 31.1 0C It is the critical temperature of CO2. The isotherm at this temperature is called critical isotherm. The portion EF represent the PV curve of gaseous CO2. At F, the liquid CO2 appears. Here the gas and liquid have the same density and are indistinguishable. This point is known as the critical point and the corresponding pressure is known as critical pressure. Van der Waals Equation and Critical Constants The van der Waals equation for one mole of a gas is ,

Rearranging,

This is a cubic equation in V. therefore, for a particular pressure, there may have three values for V. At the critical temperature, all the three roots of V are identical and is equal to critical volume, Vc. At critical point, V=Vc Or V-Vc=0 Or (V-Vc)3 = 0 V3 3VcV2 + 3 Vc2V-Vc3 = 0 This equation is identical with the van der Waals equation given in the form of the cubic equation of V. Thus when T=Tc and P =Pc, the equation can be written as,

Equating the coefficients of V terms, we get