24 point, For higher densities, aditional tens can be used and deter. ‘mined empirically ‘Computers allow the use of very complex equations of state in calculating p-v-P values, even to high densities. The Benedict ‘Webb-Rubin (B-W-R) equation of state (Benedict etal. 1940) and “Martin-Hou equation (1955) have had considerebe use, but should ‘generally be limited to densities less than the ertical value, Stto- bridge (1962) suggesied « modified Benedict-Webb-Rubin relstion that gives excelent results a higher densities and ean be used for@ paeT sutfae that extends int the liquid phase. "The B-W-R equation has been used extensively for hydrocarbons (Cooper and Goldfrank 1967) P= (RI) +(B,8T-4,-C/P Vv? + (bRT~a)/0° + (aay/r® + fet eV YT? (23) where the constant coefficients ae Ay By Cyr by 6, andy "The Marin-Hou equation, developed for lorinaied ydro- carbon properties, has been Used to caleulte the thenmodyraic propery tables in Chapter 30 and im ASHRAB Thermodynamic Properties of Refrigerants (Stewart etal. 1986). The Martin-Fou equation is an Ape Byr eal apeayrvclt Pe Bb 2 7 (by (by carry AyL BAT Ag+ BPs Ce p Ae Bat As BSTC ag Bre (24) 0) =) here the constant coefficients ae 4, B), Cy, band a Strobridge (1962) suggested an equation of state that was devel- ‘oped for nitrogen properties and used for most eryogenic fuds. ‘This equation combines the B-W-R equation of state with an equa- tion for high-density nitrogen suggested by Benedict (1937), These ‘equations have been used successfully for liquid and vapor phases, extending inthe liquid phase to the tple-point temperature and the freezing lie, and in the vapor phase from 10 to 1000 K, with pres sures to 1 GPa, The Stobridge equation is accurate within the uncertainty ofthe measured p-i- data p= RTp+|RmyT+my+id+ 2 eB] Tap + (RngT + my)e° + ngTp* ei tem ra @s) ae mT Selene r ‘The 15 coefficients ofthis equation’s linear terms ae determined bby a least-square fit to experimental data, Hust and MeCarty (1967), and Hust and Stewart (1966) give further information on methods tnd techniques for determining equations of sate In the absence of experimental dat, Van der Waals’ principle of comesponting states can predict fuid properties. This principle relates properties of similar substances by suitable reducing factors (ie, the pa-T surfaces of similar Muids in a given region are assumed tobe of similar shape). The eritcal point ean be used to define reducing parameters to scale the surface of one fluid tthe «dimensions of anather. Modifications ofthis principle, as suggested by Kamerlingh Onnes, a Dutch eryogenic researcher, have been used ta improve correspondence at iow pressures, The principle of 2009 ASHRAE Handbook—Fundamentals (SI) corresponding states provides useful approximations, and numer ‘ous modifications have been reported. More complex treatments for predicting properties, which recognize similarity of fui properties, are by generalized equations of state. These equations ordinarily, allow adjustment of the p-v-T surface by introducing parameters. ‘One example (Hirschfelder eta, 1958) allows for depareures from, the principle of coresponding states by adding ovo correlating parameters CALCULATING THERMODYNAMIC PROPERTIES. Although equations of state provide p-v-T relations, thermo- dynamic anelysis usvally requites values for intemal energy, cethalpy, and entropy. These properties have been tabulated for ‘many substances, including refrigerants (see Chapters 1, 30, and 13), and ean be exacted from such tables by interpolating manu ally or with a suitable computer program. This approach is appro priate for hand calculations and for relatively simple computer ‘models; however, or many computer simulations, the overhead in ‘memory of input and output required to use tabulated data can ‘make this approach unacceptable. For large thermal system simu- lations or complex analyses, it may be more efficient to determine intemal energy, enthalpy, end entropy using fundamental thermo- dynamic relations or curves fitto experimental data. Some ofthese relations are discussed in the following sections. Also, the th ‘modynamic relations discussed in those sections are the basis for constructing tables of thermodynamic property data. Further formation on the topie may be found in references covering system modeling and thermodynamics (Howell und Buckius 1992; Stoecker 1989), At least two intensive properties (properties independent ofthe {quantity of substance, such as temperature, pressure, specific vol~ ume, and specific enthalpy) must be known to determine the remaining properties. IF wo known properties are ether p, », of T (these are relatively easy to measure and are commonly used in simulations), the third ean be determined throughout the range of interest using an equation of state, Furthermore, ifthe specie heats at zero pressure are known, specific heat can be accurately, determined from spectroscopic measurements using statistical ‘mechanies (NASA 1971). Entropy may be considered a funtion of T and p, end from calculus an infinitesimal change in entropy can be writen as ds = (26) Likes, hangs in emda an be wten as ou = (2 ar op @ Using the Gibbs relation Tl cific heat at constant pressure, rearranged 0 yield _ egy [28] Jee ts = Bar (a, i es Equations (26) end (28) combine to yield (2/97) = ¢y/T Then, using he Maxwell elation (65'@p),=—(Gu/éT),, Equation (26) may ‘be rewriten as thvdp and the definition of spe- (Qh/GT), Equation (27) can be Par {2) ds = fat &l dp 2 ‘This is an expression for an exact derivative, soi follows thet,