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The Law of Corresponding States The Principle of Corresponding States as stated by Van Der Waals: Substances behave alike at the same reduced states. Substances at same reduced states are at corresponding states. Therefore all fluids, when compared at the same reduced temperature and reduced pressure, have approximately the same compressibility factor, and all deviate from the ideal gas behaviour to about the same degree. This law is more accurate if the gases have similar molecular characteristics. Since most of the gases the petroleum engineer deals with are composed primarily of molecules of the same class of organic compounds known as paraffin hydrocarbons, the theory holds true. The Law of Corresponding States was extended to cover mixtures of gases which are closely related. However, obtaining the critical point for multicomponent mixtures was somewhat difficult; which eventually lead to the development of pseudocritical temperature and pseudocritical pressure. These quantities are defined as: T pc = y i Tcj and Ppc = y j Pcj . j j Where y i is the mole fraction of the i-th component, Tcj and Pcj are the pseudocritical temperature and pseudocritical pressure of the individual components of the gas mixture. These two equations are often referred to as Kays mixture rules. The pseudocritical properties were devised simply for use in correlating physical properties, since pseudocritical properties are not equal to the actual critical properties of a gas mixture. Physical properties of gas mixtures are correlated with pseudoreduced temperature and pseudoreduced pressure.
T P , Ppr = , T pc Ppc
T pr =
It is used extensively for thermodynamic correlations, which is its most popular application. Most thermodynamic correlations have been made viable and general because of the application of the principle of corresponding states. An example is the popular Z-chart of Standing and Katz, shown in Figure 1 below. This chart allows us to determine the gas compressibility factor for a real gas, which is used in the EOS: pV = znRT. Where z represents [vol. of real gas/vol. of ideal gas] p. This equation can then be manipulated to calculate Vg, g, Bg, Eg, Cg and other thermodynamic fluid properties.
Figure 1: Standing-Katz Compressibility Factor Chart (Reference: Standing and Katz, Trans. AIME, 1942)
Problem: Calculate viscosity using Lee et al correlation for: Specific Gravity(s.g.) 0.55, 0.72, 0.88 And discuss any trends observed. Solution:
S.G. Mw (lb/lbmole) Ppc (psia) Tpc (R) Tabs (F) Tabs (R) Pabs (psia) Ppr Tpr z factor (g/cc) X K Y g (cp)
0.55
15.93
672
334
0.72
20.85
660
382
150 610 1500 170 630 1815 195 655 2000 * Optimized LGE variables were used in the calculation of X, K, and Y. Mw of Air = R (lb-mole R) = 28.96 10.732
0.80
23.17
650
400
Variable k1 k2 k3 k4 k5 x1 x2 x3 y1 y2
Original LGE 9.379 0.01607 1.5 209.2 19.26 3.448 986.4 0.01009 2.447 0.2224
Optimized LGE 16.717500 0.041919 1.402560 212.209000 18.134900 2.125740 2063.710000 0.001193 1.098090 -0.039285
Procedure for the Determination of Gas Viscosity using Lee, Gonzalez, and Eakin, Correlation (Lee, et al): Using the specific gravity, values of the pseudocritical temperatures (Tpc) and pressures (Ppc) were read off from a graph of pseudocritical temperature and pressure vs. specific gravity (Fig.2) Using these values the reduced temperatures and pressures were then calculated using the following equations: Ppr = Pabs/ Ppc and Tpr = Tabs/ Tpc Using Fig.1 the gas compressibility factor (z-factor) was found for each value of Ppr and Tpr. The gas density was then calculated using the following equation:
g =
Where, Mw = molecular weight of the gas in lb/lb-mole = S.G. of gas Mw of air R = Universal gas constant = 10.732 (psia cu ft)/(lb-mole deg R) 62.37 = Conversion constant: 1g/cc = 62.37lbm/ft3 g is in g/cc The factors X, K and Y were then calculated using the following equations:
x2 + x3 M w T (k + k 2 M w )T k3 K= 1 k 4 + k5 M w + T X = x1 + Y = y1 y 2 X
Graphs of pressure versus gas viscosity and temperature versus gas viscosity were plotted for each value of specific gravity.
Effect of Pressure on Gas Viscosity
0.0175
0.0170
0.0165
0.0160
0.0155
0.0150
0.0145 1450
1500
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050
0.0170
0.0165
0.0160
0.0155
0.0150
0.0145 605
610
615
620
625
630
635
640
645
650
655
660
Discussion of Observed Trends: Effect of Temperature on Gas Viscosity As the temperature of the gas increases so does the gas viscosity, however this increase is non-linear. Unlike liquids, the viscosity of gases increases as temperature increases and is approximately proportional to the square of the temperature i.e.
T 2 . This is due to the increase in the frequency of intermolecular collisions at
higher temperatures. Since most of the time the molecules in a gas are moving freely through the void, anything that increases the number of times one molecule makes contact with another, will decrease the ability of the molecules as a whole; to engage in coordinated movement. The more these molecules collide with one another, the more disorganized their motion becomes. At low pressures, gas viscosity increases as temperature increases, however, at high pressures gas viscosity decreases as temperature increases. Hence the effect of temperature on gas viscosity is dependent on system pressure. Effect of Pressure on Gas Viscosity Gas viscosity decreases as reservoir pressure decreases, and vice versa. The molecules are further apart at lower pressures and move past each other more easily. From the viscosity vs. pressure graph it can be seen that as pressure is increased the viscosity increases, this increase is almost linear in nature. Generally at low pressures; gas viscosity decreases as the pressure decreases since the molecules become widely separated. However at high pressures the gas behaves as a liquid as the molecules become closer together and therefore viscosity increases. Effect of Composition on Gas Viscosity It can be seen that generally as the specific gravity or molecular weight increases so does the viscosity. The higher the molecular weight the higher the viscosity. This is true for both oil and gas, since as the molecular weight increases, so does the length of the alkane chain. The increase in chain length increases the amount of cross-linkages, and hence the amount of entanglement taking place between the alkane molecules which make up the hydrocarbon resulting in more interactions and hence increased viscosity. i.e. increased resistance to flow.
. Effect of Pressure on Liquid Viscosity A decrease in pressure causes a decrease in viscosity, provided that the only effect of pressure is to compress the liquid. For reservoir fluids there is an additional parameter which affects viscosity. A decrease in the amount of gas in solution in the liquid causes an increase in viscosity, and the amount of gas in solution is also a direct function of pressure. The viscosity of a liquid is related directly to the type and size of the molecules which make up the liquid. i.e. composition.
References: Canadian International Petroleum Conference paper 2004-2004-214 Comparison of Correlations for viscosity of Sour Natural Gas. O. Jeje, L. Mattar SPE 75721- Simplified Correlations of Hydrocarbon Gas Viscosity and Gas Density- F.E. Londono, R.A. Archer, and T. A. Blasingame, Texas A&M U. The Properties of Petroleum Fluids 2nd Ed. William D. McCain, Jr. PennWell Books, PennWell Publishing Company. Tulsa, Oklahoma.