Experiment 4- Real Gases Part II: The Second Viral Coefficient

Introduction:
When considering the properties of a gas we consider the ideal gas law: PV=nRT (1) This law works under the assumption gases behave ideally; molecules of gas occupy zero volume, no intermolecular interactions between the molecules of the gas and energy is conserved for the intermolecular collisions. Realistically this is not the case, real gases are not ideal and these conditions are not always true. However under relatively high temperatures and lower pressures, gases model ideal gas behaviour. Under these conditions, the ideal gas law can be used to determine the properties of the gas. Deviations from ideal gas behaviour can be observed by keeping the number of moles of gas constant and measuring the pressure, volume and temperature of gas at equilibrium. A thermodynamic property which modifies the ideal gas law to consider behaviour of real gases is known as the compressibility factor (Z), with ideal gases having a compressibility factor of 1. (2) The extent to which Z diverges from 1 will show the deviations of ideal behaviour for a gas. As the compressibility factor is dependent on the pressure and volume of a system shown through the power series, where A2, A3, A4, B2, B3 and B4 are virial coefficients: (3) Or ( ) ( ) ( ) (4) Each virial coefficient An and Bn, are the simultaneous interactions between moles of the gas. As pressure increases or small molar volumes higher-order virial coefficients become significant, in these cases ideal gas model become inaccurate. At lower pressures the power series can be simplified to (5) and (6), as we neglect higher-order viral coefficients. (5) Or ( ) (6) The virial coefficients can be further applied to the van der Waals equation of state (7) and viral coefficients A2 and B2 can be calculated by (8) and (9): (7) ) (8) and (9) Where a and b can be determined from the temperature dependence of A2 and B2, in turn the viral coefficients can be determined from the constants. A similar approach of applying viral coefficients to the Beattie-Bridgeman Equation of State (10), where B2 can be calculated by (11) :
) )

(10)

(11) State properties of a real gas can be determined from the second virial coefficient through the equation (12), from this equation fugacity coefficient of gas can be determined (13). (12) n (13)

The second virial coefficient of CO2 was determined through measuring Z as function of pressure. This experiment consists of an apparatus of two gas cylinders, an expansion and sample cylinder with pressure, volume and temperature which can be easily calculated. Typically the number of moles of substance is determined through mass and molar mass but for gases, moles are difficult to determine through these components. Gases tend to adsorb onto the walls of the cylinders and interact with its surroundings, leading to another method to be used to determine its moles. The determination of moles for a gas is not straightforward, gas filling and handling apparatus is used. Instead the volume ratio between the two cylinders can be determined, rewriting the moleindependent equation using the volume ratio we can determine the compressibility factor. To calculate the second virial coefficient the high-pressure gas is converted to a low pressure state where the Ideal gas equation can be used. Using an equation derived from Boy es Law we can determine the volume ratio (14) Ve/Vs , which equation to use will depend on the method used to determine initial and final pressures: ( ) or ( ) (14) Using the volume ration, the compressibility factor (Z) can be determined through the equation (15) with r as the index of pressure sample and m as the other index.
)

(15)

Once Z is determined through experimental determination through various pressures of the sample cylinder, the second virial coefficient A2 can be determined. When keeping the experiment at a low pressure and large volume, higher-order viral coefficients become insignificant behaving like ideal gases. Plotting a graph between pressure and compressibility factor will form a linear graph, with the slope representing the second viral coefficient A2 and the y-intercept of Z for ideal behaviour of a value of 1. (16) Unreactive gases under practical conditions usually have a compressibility factor between 0.8 and 1, therefore a relatively small effect. The high and low voltages that were obtained can be calculated into high and low pressures by using the high pressure formula (17) and low pressure formula (18). high pressure P (psi) =59.906V-28.674 (17) low pressure P (psi) (18)

Discussion:
The second virial coefficient of CO2 was determined through the linear relationship between compressibility factor (Z) and pressure. Under relatively low pressures gases can behave in an ideal behaviour, as shown through the linear relationship between pressure and the compressibility factor. The apparatus was step up in an isothermal condition, with temperature constant. Results that was obtained from the lab was consisted with the theory, because the more negative the A2 coefficient value is the more reduced the pressure is due to the interacting intermolecular forces. Expected results were determined through the calculations of the viral coefficients, leading to erroneous viral coefficient. The relationship of the compressibility factor and pressure had a negative slope as expected, with a y-intercept of close to 1. The slope of the relationship provides the second viral coefficient A2, with a value of -0.000351 and a y-intercept value of 1.016. The y-intercept provides information about the compressibility factor for a particular gas, in this case 1.016 indicates the gas behaved similarly to a ideal gas with a value close to 1. The value of B2 that was calculated was positive. The expected value for B2 was negative as calculated using the van der Waals and Beattie-Bridgeman equations of state as well as from the linear interpolation. Errors in the results determined in the lab can be traced back to apparatus and instruments used. The pressure transducers had uncertainties; when recording the voltages of the high pressure transducer is increased rapidly as the valves could only be tighten to a certain extent. When handling the valves, gas may have leaked if the valves were not closed perfectly. Major cause of error was the determination of the volume ratio for the expansion and sample cylinders. The error determined in the virial coefficient was for the most part caused by step up of the apparatus in the lab.