A Critical Point Anomaly In Saturation Curves Of Reduced Temperat

The Space Congress® Proceedings 1971 (8th) Vol Technology Today And Tomorrow Apr 1st, 8:00 AM A Critical Point Anomaly In Saturation Curves Of Reduced Temperatures -Compressibility Planes Of Pure Substances Joseph W Bursik Associate Professor of Aeronautical Engineering and Astronautics, Rensselaer Polytechnic Institute Follow this and additional works at: https://commons.erau.edu/space-congress-proceedings Scholarly Commons Citation Bursik, Joseph W., "A Critical Point Anomaly In Saturation Curves Of Reduced Temperatures -Compressibility Planes Of Pure Substances" (1971) The Space Congress® Proceedings https://commons.erau.edu/space-congress-proceedings/proceedings-1971-8th/session-4/5 This Event is brought to you for free and open access by the Conferences at Scholarly Commons It has been accepted for inclusion in The Space Congress® Proceedings by an authorized administrator of Scholarly Commons For more information, please contact commons@erau.edu A CRITICAL POINT ANOMALY IN SATURATION CURVES OF REDUCED TEMPERATURE COMPRESSIBILITY PLANES OF PURE SUBSTANCES Joseph W Bursik Associate Professor of Aeronautical Engineering and Astronautics Rensselaer Polytechnic Institute Troy, New York ABSTRACT in luring away adherents of the classical view, Lines of striction are obtained in 9, x, Tr and Z, x, Tr spaces of one component, two-phase re­ gions; being the reduced pressure volume prod­ uct, pr vr ; Z, pr vr/Tr and x the quality Us­ ing the concept of smoothly joined saturation curves at the critical points of Tr , and Tr , Z planes and a transformation of the striction curves into the 9, Z plane results in an impos­ sible anomaly at the critical point Removal of the anomaly necessitates abondoning the concept of smooth, saturation curves at the critical points of all of these planes In this paper a new, analytical approach is used to revive the concept of a critical point at which the saturation curves are joined non- smoothly This method uses the combined disciplines of metric dif­ ferential geometry and thermodynamics It utilizes as its chief tool the geometric concept of the line of striction associated with the representation of various thermodynamic functions as ruled, non- de­ velopable surfaces These functions are the re­ duced compressibility factor and the reduced pres­ sure-specific volume product Extended Geometrical Surfaces INTRODUCTION In the classical thermodynamics conception of the critical point terminating the liquid-vapor re­ gion of an arbitrary pure substance the coexis­ tence curves are always smoothly joined when the properties are viewed in appropriate planes In the pressure - specific volume plane a horizontal line through the critical point serves as the tangent line to both the saturated liquid and va­ por curves A similar statement can be made with regard to the joining of the coexistence curves at the critical point of any plane in which pres­ sure or temperature is plotted as the ordinate and any function such as the compressibility or the specific value of entropy, internal energy, enthalpy, volume, etc., is plotted as the abscis­ sa Indeed, when any two functions from this lat­ ter group are cross plotted - as for example in the Mollier plane - the smoothness concept at the critical point is still retained However, the common critical tangent to the saturated liquid and vapor curves is no longer a horizontal line in these planes In spite of the general acceptance of this con­ cept of critical point smoothness; other views have appeared in the literature from time to time These range from a critical temperature line con­ cept ^ to a non-smooth point concept Mayer and Harrison,(2,3) for example, envisioned a rather narrow spike of two-phase region added in the vicinity of the critical point to the normal twophase region of the p, v plane; and CallenderW reported strong discontinuities in the saturation curve slopes at the critical point However, these departures from the classical thermodynam­ ics smoothness concept have not been successful 4-1 In the liquid-vapor regions of pure substances the mixture specific volume can be written explicitly as a function of the quality and implicitly as a function of the temperature through the dependence of the saturated liquid and vapor volumes on the temperature Thus, v(x,T) = V THE LINE OF STRICTION (8) and (9) The saturated vapor and saturated liquid values of these functions are respectively (10) (11) Fr V 2r and (p r /T r')v, vt JLr*, (12) P v rl, *r (13) From these and the fact that the pressure is a func­ tion of the temperature, the isothermal phase change values are formed as Z 12 = (pr/Tr)v!2r (14) For the case of interest of this paper, y-^ will vary with the temperature; thus, the extended geo­ metric surface given by Equation 18 is a non-devel­ opable, ruled surface As such, it has the proper­ ty that as the contact point of the surface normal moves on a ruling from minus infinity to plus in­ finity the normal simultaneously rotates about the ruling through an angle oftf with the rotation being continuous and in one direction only This means that at some intermediate contact point of the same ruling the surface normal must be turned through an angle ofTT/g relative to its orientation at either infinity of the ruling This intermediate contact point is called the central point of the ruling Thus each ruling has a central point and the locus of the central points is defined as the line of striction This curve which spans the entire tem­ perature interval of the two-phase region because the rulings of the surface of Equation 18 are the isotherms is of fundamental importance to two-phase thermodynamics It will be derived from the proper­ ties of the surface normal already described The total differential of y is obtained from Equa­ tion 18 as dy = and Pr V12r (15) When these are substituted into Equations and the results are l:m:n (16) (17) 0:4-1:0 These two equations have the same form and from a geometrical point of view they will be treated when­ ever possible as one equation of the form y(x,Tr) (20) !2 : yl When the quality approaches plus or minus infinity on an isotherm not the critical, the above relation becomes and 12 (19) From this, the direction cosine ratios for the sur­ face normal are read as (18) That is, if y is replaced everywhere in Equation 18 by Z, Equation 16 results; similarly, substitution of for y in Equation 18 gives Equation 17 (21) That is, the surface normals at the two infinities of the isothermal ruling are parallel and anti-par­ allel to the Tr axis This means that the surface normal is rotated 180° at the second infinity rela­ tive to the first To obtain an expression for the contact point cor­ responding to the central point it is only neces­ sary to set Equation 18 represents a ruled surface in y, x, T space with the reduced isotherms being the rulings, and x being the quality When yj^ *- not a constant the surface is non-developable Ordinarily the qual­ ity is restricted to the physical interval between zero and one, in effect restricting the rulings to a finite extent However, an extended geometric surface is obtainable from Equation 18 by merely per­ mitting the quality to take on values from minus in­ finity to plus infinity In this way the rulings of the usual thermodynamic surface are extended to infinite length and the ordinary thermodynamic sur­ face becomes a sub-surface of the extended geomet­ rical surface (22) Xey y!2 at the central point whose quality is now denoted by xey With this, the direction cosine relation at the central point is obtained from Equations 22 and 20 as ey "12 - As previously mentioned the locus of the central 4-2 (23) Comparison with Equation 21 shows that the surface normal at the central point of the ruling is orient­ ed at an angle of 90° from the normals at the two infinities of the same ruling points is the line of striction, a space curve whose x, Tr trace is given by Equation 22 Since y^ and y12 are temperature functions, it is expected in general that Equation 22 defines xe as a function of temperature except in a possible special case where y{(Tr> is proportional to y{ (Tr) If this case were possible, then x would be a constant and the surface becomes a conoid or even a right helicoid - surfaces that are well understood in met­ ric differential geometry With Equations 18 and 22 the formal description of the line of striction becomes (24) ['