Problem 2.1.1

 

What is the specific volume of isopropanol vapor at 250 degrees Centigrade and 106 atmospheres?  Critical temperature is 508.15 Kelvin and critical pressure is 53 atmospheres?

 

Solution: 

 

The nonideality of a gas is conveniently expressed by the compressibility factor, Z: that is equal to PV/RT where V is equal to molar volume, P is absolute pressure, T is absolute temperature, and R is universal gas constant.  The gas constant R assumes different values for different sets of units. 

 

Values of the Gas constants R are 83.144 bar cm3 per mole per Kelvin; 8.314 Joules per mole per Kelvin; 82.057 atmosphere cm3 per mole per Kelvin; 0.08206 atmospheres liters per mole per Kelvin. 

 

For an ideal gas Z is equal to 1.0.  For real gases, Z is normally less than 1 except at high reduced temperatures and pressure.  The compressibility factor is often correlated with the reduced temperature Tr and pressure Pr as Z is equal to function of Tr and Pr.  In this function Tr is equal to T over Tc and Pr is equal to P over Pc.  The function f( ) has been obtained from experimental PVT data and the final curves given in the literature as figures. 

 

Except as noted below, the use of these figures to obtain Z at given Tr and Pr should lead to errors  of less than to 4 to 6 percent except near the saturation curve or near the critical point, where Z is very sensitive to both Tr and Pr.  These figures should not be used for strongly polar fluids, nor are the recommended for helium, hydrogen, or neon unless special, modified constants are used.        

 

For ideal gases, pV is equal to RT where p is total pressure, V is the volume and T is temperature.  R is the universal gas constant.  Pay attention to the numeric values of this constant.  If we consider that pV is equal to ZRT where Z is the compressibility factor and is given by two parameters, reduced pressure, Pr, and reduced temperature, Tr, then the value of this compressibility factor could be found by any compressibility factor chart, like the one provided by Hougen & Watson.

 

These reduced values are defined as ratio of absolute value to the critical value.  For the present situation, reduced pressure is 106 over 53 and is equal to 2.  Reduced temperature is 523.15 over 508.15 and is equal to 1.03.  Now we can get the value of Z from the chart as a function of reduced pressure with reduced temperature as a parameter.  It is found to be equal to 0.33.

 

The value of R is equal to 0.08206 atmospheres liters per mole per Kelvin.  Volume of the vapors is equal to ZRT over P and is calculated to be 0.142 liters per mole.