i | i w = u = & £ Z W \ fi:l | | m | ll; 1| MARTiH MARL | ORNL.2677 Reactors—Power TiD-4500 (14th ed.) Contract No, W-7405-eng-26 REACTOR PROJECTS DIVISION ALUMINUM CHLORIDE AS A THERMODYNAMIC WORKING FLUID AND HEAT TRANSFER MEDIUM M. Blander, L. G. Epel, A. P. Fraas, and R. F. Newton DATE ISSUED SEP 911959 OAK RIDGE NATIONAL LABORATORY Uak Ridge, Tennessece - opesated b UNION CARBIDE CORFORATION for the U.5. ATOMIC ENERGY COMMISSION MARTIN MARIETTA ENERGY SYSTEMS LIBRARIES R 3 4456 03LL3LY O ALUMINUM CHLORIDE AS A THERMODYNAMIC WORKING FLUID AND HEAT TRANSFER MEDIUM M. Blander L.. G. Epel A. P. Fraas R. F. Newton ABSTRACT The basic physical properties ond thermodynamic constants of aluminum chloride have been calculated to obtain the data required for engineering calculations of thermodynamic cycles employing aluminum chloride vapor. The possible corrosion problems invelved were evaluated from the standpoint of basic chemical thermodynamics, and it was concluded that high-nickel- content alfoys would contain aluminum chloride satisfactorily. The advantages of gaseous aluminum chloride as an intermediate heat transfer medium in a molten-salt-fueled reactor were evaluated. It was determined that the temperature range of the molten-salt heat transfer system was too low to utilize aluminum chloride effectively. A gas. turbine cycle employing aluminum chleride as the working fluid and a binary vapor cycle employing water vapor for the lower temperature cycle were also considered. Meither of these studies showed aluminum chloride to have outstanding advantages. It is believed, however, that special appli- cations may be found in which it will be possible to exploit the unique characteristics of aluminum chloride. INTRODUCTION Gaseous aluminum chloride appears to be attrac- tive as a heat transfer medium and as a thermeo- dynamic-cycle working fluid as a consequence of the fact that it exists as the monomer AICI, at high temperatures and as the dimer A|2C|6-ct fow temperatures. The effective specific heat and thermal conductivity of a gas that associates are considerably enhanced because of the association equilibrium at temperatures ot which there is an appreciable fraction of both monomer and polymer, and therefore aluminum chloride may be an excep- tionally good heat transfer medium for some applications. Its possibilities as the working fluid in a thermodynamic cycle stem from the fact that, in an idealized gas turbine with a negligible pressure drop in the system, the pump compressor will require work proportional to the compressor inlet temperature times the specific gas constant of the dimer for any given pressure ratio. In the high-temperature region at the turbine, on the other hand, if the gas is completely monomeric, this same weight of gas will do work proportional to the turbine inlet temperature times the monomer gas constant for the same pressure ratio. Because of the relatively large difference in the gas constant between the monomer and dimer, the ratio of turbine work to compressor work will be greater than for a gos that does not dissociate. Further, the energy losses due to the inefficiency of both the compressor and the turbine will have relatively smaller effects on the over-all thermal efficiency with a dissociating gos as the working fluid. BASIC PHYSICAL PROPERTIES OF ALUMINUM CHLORIDE The objective of this study was to investigate the possible advantages of aluminum chloride arising from its dissociation and the consequent increase in effective specific heat and thermal conductivity. Qualitatively the reason for these increases is simple. Lowering the temperature of the gas will yield not only the heat given off if the composition of the gos were ‘‘frozen,”” but, since the gas is more highly associated at lower temperatures, it will also give off the chemical heat due to the association of some of the monomer molecules as a result of lowering the temperature. The same phenomenon increases the thermal conductivity. The thermal conductivity is the amount of heat that would be transferred in unit time across unit area from a temperature T + dT to 1 divided by the temperature gradient, d7/dx. The frozen thermal conductivity is that which would occur if the composition were frozen at an average weight fraction @ _ of the polymer and w, of the monomer at both temperatures. Since w, is higher at 7 + dT and w_ is higher at T than the average, relatively more monomer would diffuse from T +dT to T and more polymer from 1" to T +dT than for a frozen composition. The composition of the higher-temperature gas molecules diffusing to the lower temperature would change with a trend toward the lower equilibrium concentration of monomer at the lower temperature and would give off heat in the process. This chemical heat contribution is part of the heat flux. Quantitative expressions for these phenomena have been given by Butler and Brokaw.! For a substance which dimerizes, AH2 w]wzfl + wl) C, =C, + e (1 be v/ RT?2 4M] AHZ (PP [y, A, = A+ - : (2) € RT2A\RT /N 2 where Cpe = effective specific heat in cal.g™ .deg™ !, Cpf = frozen specific heat, AHl = heat change for the reaction —_— AlLCl = 2A1CH,, R, R* = gas constants in proper units, w, w, = weight fraction of monomer and dimer, respectively, A, = effective thermal conductivity in caleem™ Vsec™ tideg™ !, )\f = frozen thermal conductivity, D12 = interdiffusion coefficients of monomer and dimer, P = total pressure, M, = molecular weight of a monomer. ). N. Butler and R. S. Brokaw, J. Chem. Phys. 26, 1636 (1957). The guantities of practical interest, the effective specific heat, C, , the effective thermal conduc- tivity, A, and the viscosity, have never been These and other quantities of interest must be estimated. It is fortunate that the theory of gases is well developed and, for some calcu- measured. lations, is more reliable than measurements. Effective Specific Heat The effective specific heat was calculated by use of Eq. (1). The frozen specific heat of Al Cl C,, was estimated according to well-known bl . 2 statistical mechanical methods* by use of the infrared vibrational frequencies measured or esti- mated by Klemperer.® The frequencies for AlCI, were estimated by analogy with the compound E’:C!3 (ref 4). The average value of the specific heat in the temperature range 500 to 1000°K is 0.16 cal.g™.(°C)~' for ALCl, and is 0.14 cc:z]-g"]-(c(f)“1 for A|C|3. At each composition of the gas, an average value was computed from the composition-weighted average of these two values for the monomer and the dimer. The composition of the gas may be computed from the equilibrium constant , (3a) where AF® — All ~ TAS® = ~RT In K , (35) in which AH is the heat of dissociation of the gos, which was taken as 29.6 kcal/mole (ref 5), and AS® is the entropy difference between 2 moles of AICI; at 1 atm pressure and 1 mole of ALLCl, at 1 atm pressure, which was token as 34.6 cal.-mole™'.deg™! (ref 5). The values of ) calculated from Eqs. (3a) and (36) at pressures of 0.1, 1, and 10 atm, respectively, in the temperature range 500 to 1200°K ore listed in column 2 of Table 1. Column 3 of the same table lists the 2J. E. Mayer and M. G, Mayer, Statistical Mechanics, Wiley, New York, 1940, 3W. Klemperer, J. Chem, Phys. 24, 353 (1956). 4G. Herzberg, Molecular Spectra and Molecular Struc- ture, Yan Nostrand, New York, 1945, SA. Shepp and S. H. Bauver, J. Am. Chem Soc. 76, 265 {1954}). Table 1. Calculated Values of w,, cpe,if, and A for Aluminum Chloride Temperature Weight Fraction Cpe Af Ae (%) of Menomer, wy (1= Vdeg™ ) (caliem™ Lesec™ Lideg™ 1) (cabrem™Visec™ Vedeg™ ) For a Pressure of 0.1 atm % 1078 x 1078 500 0.003 0.17 12 14 550 0.013 0.19 13 18 600 0.038 0.25 13 26 650 0.100 0.35 14 42 700 0.223 0.51 15 63 750 0.422 0.66 16 77 800 0.655 0.63 17 68 850 0.831 0.43 18 47 900 0.926 0.28 19 32 950 0.966 0.20 19 25 1000 0.984 0.17 20 23 1050 0.992 0.15 20+ 22 1100 0.996 0.15 21 22 1150 0.998 0.14 21 21+ 1200 0.999 0.14 22 29— For a Pressure of 1 atm x 10~8 x 1078 500 0.001 0.16 12 13 550 ~ 0,004 0.17 13 15 600 0.012 0.19 13 17 650 0.032 0.22 14 24 700 0.072 0.28 15 34 750 0.145 0.36 15 46 800 0.264 0.47 16 60 850 0.428 0.55 17 68 900 0.612 0.54 18 63 950 0.766 0.44 19 50 1000 0.870 0.32 19 37 1050 0.929 0.24 20 30 1100 0.961 0.19 20 25 1150 0.978 0.17 21 24 1200 0.987 0.16 22 ’ 24 Table 1 {(continuved) Temperature Weight Fraction Cpe ’\f ’\e () of Monomer, 1 (cc[-g"l-deg"l) (cql-cm"']'sec'”]-deg"]) (cal-cm”]-sec“]-degwl) For a Pressure of 10 atm x 107° x 1076 500 0.000 0.16 12 12 550 0.001 0.16 13 14 600 0.004 0.17 13 14 650 0.010 0.18 14 17 700 0.023 0.20 14 20 750 0.047 0.23 15 26 800 0.087 0.27 16 34 850 0.148 0.32 16 42 %00 0.240 0.38 17 52 950 0.352 0.43 18 58 1000 0.4%90 0.46 18 59 1050 0.622 0.44 19 54 1100 0.740 0.38 20 47 1150 0.827 0.30 21 40 1200 0.888 0.25 21 33 values of € estimated by use of Eq. (1) for the three pressures and the same temperature range. A plot of Cpe and the average frozen specific heat C f vs temperature at the three pressures is presented in Fig. 1. Effective Thermal Conductivities The effective thermal conductivities were calcu- lated using Eq. (2). The frozen thermal conduc- tivities of monomer and of dimer were calculated from the equation® (1.9891 x 10~ (T/M )2 [, € 4 A - S e f ’ where M is the molecular weight of o polymer, o, is the average effective molecular diameter of 8J. 0. Hirschfelder, C. F. Curtiss, and R. B. Byrd, Molecular Theory of Gases and Liquids, pp 14, 528, 534, Wiley, New York, 1954. a polymer in angstroms, and {) is a factor which corrects for intermolecular interactions and can be calculated theoretically for simple potential functions in terms of the parameters of the potential function.” A crude estimate of 02 was made for Al Cl. and AlCI,. From electron diffraction data on A|2C|6 (ref g), structural estimates for A]Cl3 (ref 5), and the van der Waals radii of chlorine atoms, the dimensions of A|2C|6 and AICI; were estimated. By comparison of the relative dimensions of similar compounds to their effective collision diameters,? the effective collision diameters of Al,‘_)Cl‘5 and AICI; were estimated. For the For a more accurate equation see J. O. Hirschfelder, J. Chem. Pbhys. 26, 282 (1957). The use of the more accurate equation leads to only a relatively small dif- ference from the values calculated here. BL. R. Maxwell, J. Opt. Soc. Am. 30, 374 (1940). 9Hirschfeic|er, Curtiss, and Byrd, op, cit., Table {-A, pp 111112, 162. Lennard-Jones 6-12 interaction potential, € has been calculated as a function of the parameter kT/€c, where € is the depth of the potential well, The volue of ¢ is unknown for either AIZCié or AICl,. We may, however, estimate € by analogy with other halogen-containing compounds. Of several halogen-containing compounds? the lowest value of €/k is 324 for HI and the highest is 1550 for SnCl,. With these values as limits, the fol- lowing values were obtained for (: T {°K) €/k Q 500 324 1.3 1550 2.7 1000 324 1.0 1550 2.0 The range of values of O listed is 1,0 to 2.7, and a value of & = 2 was arbitrarily chosen as being reasonable. The value of D, P was estimated from the equation !9 i ]/2 0.0026280 [ M1+ M, 12 Peoon — — | T ——o ’ (5) sz % QMIMZ where M, and M, are the molecular weights of monomer and dimer, respectively, Tig= (a] + 02)/2, and 7 is o correction for intermolecular inter- actions. [t does not differ greatly from 0, and therefore the value 2.0 was used. The calculated values of I\, P in the temperature range 500 to 1200°K are listed in column 2 of Table 2. The average frozen thermal conductivities, A, and the effective thermal conductivity, A, calcu{afed' from Fa. (2), ot pressures of 0.1, 1, and 10 atm were listed in Table 1. Plots of —Xf and A_ vs tempera- ture at the three pressures are presented in Fig. 2. The constants and parameters used in these calculations are summarized below: R =1.9869 cal-mole™ T.deg™ ! R’ = 82.057 em®.atm-mole™ .deg™ ! AH = 29.6 keal for the reaction AI2C|6 === 2A|C|3 AS®=34.6 e.u., entropy change for reaction Al Cl, &= 2AICI, with both monomer and dimer at their standard state of 1 atm 19pid., p 530. UNCLASSIFIED ORNL--LR-0OWG 35264R2 500 600 700 800 200 1000 1100 1200 TEMPERATURE [°K} Fig. 1. The Calculated Effective Specific Heot of Aluminum Chloride as a Function of Temperature at Three Pressures. UNCLASSIFIED ORNL —~ LR DWG 397132 __ 8o [—~' T T T T ’g 70 L )_\9 ,,,,,,,,,,,,,, g R Tl BO bmevreemebeeeeeeee e AN L R o I S B0 e P N N N T 40 5 3 - 30 ___________ 1 Q < + 2 o 10 ............... Sreesmemmrssrmsesccsooseego ~< | ) O —— 500 600 700 800 200 1000 1100 1200 TEMPERATURE {°K) Fig. 2. The Calculated Effective Thermol Conductivi- ties of Aluminum Chloride as a Function of Temperature at Three Pressuyres. o2 = 40 A2 o2 - 65 A2 02, =51.7 A2 M, =M,/2=133.35 g/mole Q=0 =20 Cv = Cp - R Viscosity The viscosity was estimated from the equation® 2.6693 x 105 (M _T) 1/2 N, = (6) 5 a2 n Table 2. Valves of Dyy P, 74, and 175 T Dy, P Viscosity of Monomer, 17, Viscosity of Dimer, 7, (°K) (cmz-atm-sec" } (g-cm“1-sec" ) (geem™ 'esec” ) x 10™3 x 107° x 1076 500 21.3 36 75 550 24.6 g0 79 600 28.0 94 82 650 31.6 98 86 700 35.3 102 89 750 39.2 106 92 8060 43.1 109 95 850 47,2 112 98 900 51.5 116 101 950 55.8 119 103 1000 60.3 122 106 1650 64.8 125 109 1100 69.6 128 111 1150 74.3 131 114 1200 79.2 134 116 for both monomer and dimer. The calculated values are listed in columns 3 and 4 of Table 2. mixture For a of monomer and dimer, a composition weighted average would be an adequate approxi- mation to the viscosity. Vapor Pressure The vapor pressure of solid aluminum chloride in equilibrium with the gaseous phase may be calculated from the equotion'! | P(T)_~6360 og P (atm) = - +3.77 log T — ~ 0.00612T7T + 6.78 . (7} The vapor pressure is 1 atm at 180°C {453°K). VYelocity of Sound in Aluminum Chleride The velocity of sound, Cor in the working fluid is needed for turbine design. At frequencies low 0. Kubaschewski and E. L. Evans, Metallurgical Thermochemistry, Wiley, New York, 1956, enough so that the velocity of association and dissociation of the aluminum chloride is fast enough to follow the compression and rarefaction of the gas, the velocity of sound may be calcu- lated from® 2 ~1 co._ . 8 ° (ov/oP), ' ® where C is the velocity of sound in cm/sec, v is the specific volume of the gas in cm>/g, P is the pressure in dynes/cm2, and § is the entropy. The value of (au/ap)s can be calculated from the exact thermodynamic relation!? ; Ov ‘O \2 (@L) H(_é_) 4_1.(3__) (9) or /. \op c, \oT /p AT pe 12(3. N. Lewis and M. Randall, Thermodynamics and the Free Energy of Chemical substances, p 164, McGraw- Hill, New York, 1923. and the equation 1 T po=|— ') RT (10) Mz in which the reasonable assumption is made that the gaseous monomer and dimer individually behave as ideal gases and that all deviations from an ideal gas are due to the association or dissoci- ation of the goseous monemer or dimer. An evalu- ation of (dv/dP) . and (du/3T), from Eq. (10) and the thermodynamic relation dlnk A dln [4w$1’/(] - w%)] dT 2 aT (1 leads to /av v ZU.ILU2 ) = (14 JP)p P 2 and av> v( A11w1wz> 3T), T \ RT 2 ]+w ) 5 14/ R i AH Y12 —_— 14+ — . (13) P M2 RT 2 Substitution of Egs. (12) and (13) into Eq. (9} leads to L. RT (1 +wI> [ wyw, -5 P /¢ p2 M, 2 R(1 +wl) < AH w‘wz)zl - | T 4 e . (14) M, Co RT 2 _ THERMODYNAMIC PROPERTIES In the gaseous phase the state of an equilibriuvm mixture of AlCl, and AICI, is determined by any two independent properties, and knowledge of the thermodynamic state makes it possible to determine the thermodynamie properties. The two independent defining properties fraction of monomer, enthalpy, entropy, and specific used to calculate weight volume were temperotuwre and pressure. The relations used in the computational procedure are summarized below. Determination of Weight Froction of Monomer, wy. =~ It hos been shown by Newton, from free- energy-change relationships, that 1 1 1/2 w] = (—5 +—2—tanh u) ' (]5) where 1 P 13420 u=8.016 ~ —1In - , 2 14.6%96 T T is in °R, ond P is pressure in psia. Determinction of Enthalpy, 5. — The enthalpy of the mixture is the sum of the enthalpy the gas would have if it were all in the dimer state plus the enthalpy of dissociotion. Choosing absolute zero temperature as the base for enthalpy and 0.1575 Btu.1b~ 1.(°R)~ ' as the frozen specific heat averaged for the temperatures and pressures under consideration, the ‘‘sensible” enthalpy, in Btu/lb, is b, = 0.1575T . The enthalpy of dissociation is 199.7 Btu for each pound of A|2CI6 monomerized. Therefore the total enthalpy is h=0,1575T + 199.71,0] . (16) Determination of Entropy, s. — From the definition of entropy in Btu.lb~ L(°R)™ 1, erevarsible ds = ' T it can be shown'? that du + P dv ds = T Noting that dh =du+ P dv +v dP gives dbh — v dP ds = o 5 13568, for instance, J. H. Keenan, Thermodynamics, p 85, Wiley, New York, 1941, Then, for an isobaric process, that is, constant pressure, T 2 db Ab ,_\s]';‘zf — 17) T T T for small variations in T, where 1 and 2 are thermo- dynamic states. The entropy was considered equal to zero at 900°R and 150 psia, and the entropy ai other temperatures at this pressure was approximated by a stepwise, finite-difference procedure using the approximation given above. To get the entropy at 900°R and some other pressure, it is possible to use one of Maxwell’s relations '4 s\ jo (), = ~{3), \ % For a constant temperafure process, then Py s ,\s]? = wf ? (—-L-> dP o1, Py NP As shown below, tf I’ is expressed in pounds per square foot (psf), T v =5.793(1 +u,) = Since (1 + u,) does not vary from unity by more than about 0.3% at 900°R for the pressures under consideration, it can be stated that T 5.793 ) so that at constant temperature \ P35.793 A\slt = ~ —dr 1 p 9 Pl =5793 In— in ft-lb-lb~= 1.(°R) ™! P2 P] = 0.007444 In—— in Btu.lb™ LERY! P2 14,04, p 342. Determination of Specific Volume, v. —~ The perfect gas law states that RO - Pv=—T, (18) ! m where R, = 1545 ff-lbf-mole”]e(oR)"“! , and M_ is the molecular weight of the mixture and is 266??7/(1 + w]). Numerically this becomes T v=5793(01 4 w)) - inft3/lb P ¥ where P is expressed in psf, or T v=0.00023(1 + w))— inft’/lb, where P is in psia. Example of Numerical Procedure. — As an example of the calculational procedure employed, a compu- tation of weight fraction of monomer, w,, enthalpy, h, entropy, s, and specific volume, v, at a pressure of 30 psia and a temperature of 1260°R follows: 1. For the weight fraction of monomer calcu- lation, /1 1 \N1/2 Wy = (——+—-fon'r| u) , 2 2 ; where | P 13420 ©=8.016 ——in-—— 2 14.696 T ] 30 13420 = 8.016 —— In - 2 14.696 1260 = —2.9923 ond therefore 11/2 1 1 _____ + —tanh (~2.9923) 2 2 Wy o= 1 = 0.05055 2. For the enthalpy calculation, b= 0.15757 + 199.7u | = (0.1575 x 1260) + (199.7 x 0.05055) - 208.53 . 3. For the entropy calculation, at a constant pressure, AS]% 0y —— T __ 208.53 — 203.79 1260 A2 0.003792 und s ~ 0.07298 . 4. For the specific volume calculation T v = 0.04023(1 + w1)—P- 1260 - 0.04023(1 + 0.05055) —— = 1.7751 Data obtained for these functions at temperatures from 900 to 2000°R and pressures of 1.5, 5, 15, 30, 60, 100, and 150 psia are listed in Table 3, and an enthalpy-entropy chart is presented in Fig. 3. CORROSION BEHAVIOR The corrosiveness of the gas is another important consideration. The free energies of formation of aluminum chloride and the chlorides of some possible container materials at 500 and 1000°K UNCLASSIFIED ORNL-LR--DWG 39596 500 |—— 450 [ 400 |- 3150 300 ENTHALPY {Btu/Ib) 250 200 - 5'\ 0\ ‘SO \SJ 1 \(p 0.15 0.20 0.25 .20 ENTROPY [Bm gt (GR)—A] Fig. 3. Enthalpy-Entropy Diagram for Aluminum Chloride Vaper. Table 3. Thermodynamic Data for Aluminum Chloride at Various Pressures Temperature Weight Fraction Enthalpy Entropy Specific Volume °R) of AICI, (Btu/Ib) (Bru b~ 1. (°R)™ ] (F3/1b) At a Pressure of 1.5 psia 900 0.00321 142.39 0.03425 24.193 920 0.00442 145.78 0.03794 24.761 940 0.00605 149.25 0.04164 25.340 960 0.00811 152.81 0.04535 25.932 980 0.01083 156.51 0.04911 26.544 1000 0.01422 160.33 0.05294 27.176 1020 0.01848 164.33 0.05686 27.836 1040 0.02382 168.55 0.06092 28.531 1060 0.03037 173.00 0.06512 29.266 1080 0.03836 177.75 0.06951 30.049 1100 0.04808 182.84 0.07414 30.892 1120 0.05973 188.31 0.07903 31.803 1140 0.07361 194.23 0.08422 32.795 1160 0.09006 200.66 0.08%976 33.882 1180 0.10933 207.66 0.09569 35.076 1200 0.13176 215,28 0.10204 36.391 1220 0.15765 223.60 0.10886 37.844 1240 0.18725 232.65 0.11616 39.448 1260 0.22072 242.48 0.12396 41.214 1280 0.25820 253.11 0.13226 43.154 1300 0.29959 264.51 0.14104 45.270 1320 0.34464 276.65 0.15023 47.560 1340 0.39288 289.42 0.15977 50.013 1360 0.44360 302.70 0.16952 52.608 1380 0.49587 316.27 0.17936 55.314 1400 0.54854 329.93 0.18912 58.091 1420 0.60041 343,43 0.19862 60.895 1440 0.65030 356.53 0.20772 63.678 1460 0.69718 369.03 0.21629 66.396 1480 0.74025 380.78 0.22422 69.014 1500 0.77900 391.66 0.23148 71.504 1520 0.81324 401.64 0.23804 73.852 1540 0.8429% 410.72 0.24394 76,052 1560 0.86851 418.96 0.24922 78.106 1580 0.89016 426.43 0.25395 80.024 1600 0.20837 433,22 0.25819 81.818 1620 0.92359 439.40 0.26201 83.501 1640 0.93625 445,08 0.26547 85.088 1660 0.94676 450.32 0.26863 86.593 1680 0.95546 455.21 0.27154 88.028 1700 0.96267 459.80 0.27424 89.405 1720 0.96863 464.14 0.27676 90.731 1740 0.97358 468,27 0.27914 92.017 1760 0.97768 472.24 0.2813%9 93.268 1780 0.98109 476.07 0.28355 94,491 Table 3 (continued) Temperature Weight Fraction Entholpy Entropy Specific Yolume R) of AICI, (Btu/1b) [Bro- 1= 1Ry~ 11 (#3/1b) At a Pressure of 1.5 psia 1800 0.98394 479.79 0.28561 95.690 1820 0.98631 483.42 0.28760 96.869 1840 0.98830 486.96 0.28953 28.031 1860 0.98997 490.45 0.29140 99.180 1880 0.99138 493.88 0.29323 100.31 1900 0.99257 497.26 0.29501 101.44 1920 0.99357 500.61 0.29675 102.56 1940 0.99443 503.93 0.29847 103.67 1960 0.99516 507.23 0.30015 104.78 1980 0.99578 510.50 0.30180 105.88 2000 0.99631 513.76 0.30343 106.98 At a Pressure of 5 psia 900 0.00174 142.10 0.02530 7.2476 920 0.00242 145.38 0.02886 7.4135 940 0.00331 148.71 0.03241 7.5814 960 0.00444 152.08 0.03592 7.7515 280 0.00593 155.53 0.03944 7.9247 1000 0.00777 159.05 0.04296 8.1012 1020 0.01012 162.67 0.04650 8.2825 1040 0.01305 166.40 0.05010 8.4694 1060 0.01662 170.26 0.05374 8.6627 1080 0.02102 174.29 0.05747 8.8643 1100 0.02636 178.50 0.06130 9.0757 1120 0.03274 182.93 0.06525 9.2981 1140 0.04039 187.60 0.06935 9.5343 11460 0.04947 192.57 0.07363 9.7862 1180 0.06013 197.84 0.07810 10.056 1200 0.07260 203.48 0.08280 10,346 1220 0.08712 209.53 0.08776 10.661 1240 0.10384 216.01 0.09299 11.003 1260 0.12300 222.99 0.09852 11.374 1280 0.14484 230.49 0.10438 11.779 1300 0.16951 238.56 0.11059 12.221 1320 0.19714 247.23 0.11715 12,703 1340 0.22784 256.50 0.12408 13.226 1360 0.26166 266.40 0.13135 13.793 1380 0.29850 276.90 0.13895 14.404 1400 0.33816 287.96 0.14686 15.060 1420 0.38032 299.52 0.15500 15.756 1440 0.42452 311.49 0.16332 16.489 1460 0.47013 323.74 0.17171 17.254 1430 0.51642 336.12 0.18007 18.041 1500 0.56258 348,48 0.18831 18.841 1520 0.60782 360.66 0.19632 19.645 i Table 3 {(continued) 12 Temperature Weight Fraction Enthalpy Entropy Specific Velume (°R) of AICI, (Btu/Ib) [Btu-1b~1.CR)™ ] (/1) At a Pressure of 5 psia 1540 0.65132 372.48 0.20400 20.442 1560 0.69243 383.84 0.21128 21,223 1580 0.73062 394,60 0.21810 21.981 1600 0.76553 404.72 0.22442 22.708 1620 0.79699 414.15 0.23024 23.401 1640 0.824%7 422.88 0.23556 24,059 1660 0.84940 430.94 0.24042 24.681 1680 0.87106 438.37 0.24484 25.268 1700 0.88963 445.23 0.24887 25.823 1720 0.90560 451,56 0.25256 26,348 1740 0.91926 457.44 0.25593 26.845 1760 0.93093 462.92 0.25%05 27.319 1780 0.94085 468.05 0.26193 27.771 1800 0.94929 472.88 0.26461 28.205 1820 0.95645 477.46 0.26713 28.624 1840 0.96254 481.82 0.26950 29.028 1860 0.96771 486.01 0.27175 29.421 1880 0.97211 490.03 0.27389 29.804 19200 0.97586 493.93 0.27594 30.178 1920 0.97906 497.72 0.27792 30.545 1940 0.98179 501.41 0.27982 30.906 1960 0.98413 505.03 0.28167 31.261 19806 0.98614 508.58 0.28346 31.612 2000 0.98786 512.07 0.28521 31.959 At a Pressure of 15 psia 900 0.00100 141.94 0.01713 2.4140 920 0.00141 145.18 0.02064 2.4686 940 0.00189 148.42 0.02409 2.5235 960 0.00256 151.71 0.02751 2,5789 930 0.00342 155.03 0.03090 2.6349 1000 0.00448 158.39 0.03426 2.6915 1020 0.00586 161.81 0.03762 2.7491 1040 0.00753 165,30 0.04097 2.8077 1060 0.00959 168.86 0.04433 2.8676 1080 0.01215 172.52 0.04772 2.9291 1100 0.01522 176.28 0.05114 2.9923 1120 0.01891 180.17 0.05461 3.0578 1140 0.02335 184.20 0.05815 3.1260 1160 0.02858 188.40 0.06176 3.1971 1180 0.03475 192,78 0.06548 3.2717 1200 0.04199 197.37 0.06931 3.3505 1220 0.05043 202.21 0.07327 3.4339 1240 0.06017 207.30 0.07738 3.5226 1260 0.07137 212.69 0.08145 3.6172 Table 3 (continued} Temperature Weight Fraction Enthalpy Entropy Specific Volume (°R) of AICL, (Btu/1b) [Btu-lb*]-(c’R)"l] (Ft?’/ib) At a Pressure of 15 psia 1280 0.08421 218.40 0.08611 3.7186 1300 0.09882 224.46 0.09078 3.8276 1320 0.11532 230.90 0.09564 3.9449 1340 0.13388 237.75 0.10077 4.0713 1360 0.15464 245.05 0.10613 4.2077 1380 0.17770 252.80 0.11175 4,3549 1400 $.20313 261.02 0.11762 4.5134 1420 0.23099 269.73 0.12375 4.6839 1440 0.26129 278.92 0.13014 4.8668 1460 0.29395 288.59 0.13676 5.0621 1480 0.32831 298.69 0.14359 5.2697 1500 0.36567 309.20 0.15059 5.4891 1520 0.40421 320.04 0.15772 5.7192 1540 0.44404 331.13 0.16492 5.9588 1560 0.484467 342.39 0.17214 6.2061 1580 0.52559 353.70 0.17930 6.4589 1600 0.56622 364.96 0.18634 6.7148 1620 0.60601 376.04 0.19318 6.9715 1640 0.64443 386.86 0.19977 7.2264 1660 0.68101 397.31 0.20607 7.4773 1680 0.71540 407.32 0.21203 7.7222 1700 0.74732 416.84 0.21763 7.9595 1720 0.77661 425.83 £.22285 8.1881 1740 0.80320 434.28 0.22771 8.4073 1760 0.82712 442.21 0.23222 8.6168 1780 0.84848 449.62 0.23628 8.8166 1800 0.86741 456.54 0.24023 9.0069 182¢ 0.88410 463.02 0.24379 2.1884 1840 0.89874 469.10 0.24709 9.3616 1860 0.91154 474,80 0.25015 9.5271 1880 0.92270 480.18 0.25301 9.6858 1900 0.93242 485.26 0.25569 9.8383 1920 0.94085 490,10 0.25821 9.9852 1940 0.94818 494.71 0.26059 10.127 1960 0.95454 499.13 0.26284 10.265 1980 0.95006 503.38 0.26499 10.399 2000 0.96486 507.49 0.26704 10.529 At a Pressure of 30 psia 900 0.00072 141.89 0.01197 1.2066 920 0.000%7 145.09 0.01545 1.2338 940 0.00134 148.32 0.01888 1.2611 960 0.00179 151.55 0.02225 1.2885 980 0.00241 154,83 0.02559 1.3161 1000 0.00318 158.13 0.02889 1.3440 13 Table 3 (continued) Temperoture Weight Froction Enthalpy Entropy Specific Volume °R) of AICI, (Btu/Ib) (Bt b~ 1.(°R)™ 1] (#3/1b) At a Pressure of 30 psia 1020 0.00412 161.47 0.03217 1.3722 1040 0.00534 164.86 0.03543 1.4008 1060 0.00680 168.30 0.03867 1.4298 1080 0.00857 171.81 0.04192 1.4593 1100 0.01075 175.39 0.04518 1.48%96 1120 0.01338 179.07 0.04846 1.5206 1140 0.01649 182.83 0.05177 1.5525 1160 0.02020 186.73 0.055172 1.5855 1180 0.02459 190.75 0.05853 1.6198 1200 0.02971 194,92 0.06201 1.6555 1220 0.03566 199.26 0.06556 1.6928 1240 0.04258 203.79 0.06922 1.7320 1260 0.05055 208.53 0.07298 1.7734 1280 £.05965 213.50 0.07686 1.8172 1300 0.07003 218.72 0.08087 1.8637 1320 0.08181 224.22 0.08504 1.9132 1340 0.09510 230,02 0.08937 1.9660 1360 0.11001 236.14 0.09387 2.0225 1380 0.12664 242.61 0.09856 2.0830 1400 0.14513 249.45 0.10345 2.1479 1420 0.16558 256.68 0.10854 2.2175 1440 0.18800 264.30 0.11383 2.2920 1460 0.21249 272.34 0.11933 2.3717 1480 0.23905 280.79 0.12504 2.4568 1500 0.26767 289.65 0.13095 2.5476 1520 0.29827 298.90 0.13704 2.6439 1540 0.33071 308.52 0.14328 2.7456 1560 0.36481 318.48 0.14967 2.8525 1580 0.40031 328.71 0.15614 2,9642 1600 0.43692 339.16 0.16268 3.0802 1620 0.47426 349.76 0.16922 3.1998 1640 0.51192 360.42 0.17572 3.3220 1660 0.54945 371.06 0.18213 3.4460 1680 0.58643 381.59 0.18839 3.5708 1700 0.62244 391.92 C.19447 3.6953 1720 0.65708 401.98 0.20032 3.8186 1740 0.65004 411.71 0.20591 3.9398 1760 0.72105 421.05 0.21122 4.0582 1780 0.74994 429.96 0.21622 4,1732 1800 0.77659 438.42 0.22093 4.2844 1820 0.80097 446.44 0.22533 4.3915 1840 0.82310 454.00 0.22%944 4.4943 1860 0.84305 461.14 0.23328 4.5929 1880 0.86095 467.85 0.23685 4.6873 1900 0.87691 474,19 0.24018 4,7778 Table 3 (continued) Temperature Weight Fraction Enthalpy Entropy Specific Yolume CR) of AICI, (Btu/Ib) [Btuib~ L.R)™ Y (3 /1b) At o Pressure of 30 psia 1920 0.82110 480.17 0.24330 4.8646 . 1940 0.90367 485.83 0.24622 4,9479 1960 0.91477 491.19 0.24895 5.0281% 1980 0.92456 496.30 0.25153 5.1054 2000 0.93318 501.17 0.25397 5.1801 At a Pressure of 60 psia 900 0.00049 141.84 0.00681 0.60320 920 0.00071 145,04 0.01028 0.61674 940 0.00093 148.23 0.01368 0.63029 960 0.00130 151.46 0.01704 0.64393 9280 0.00171 154.69 0.02034 0.65762 1000 0.00223 157.94 0.02359 0.67139 1020 0.00293 161.23 0.02682 0.68529 1040 0.00374 164.54 0.03000 0.69929 1060 0.00479 167.90 0.03317 0.71349 1080 0.00608 171.31 0.03632 0.727883 1100 0.00759 174.76 0.03946 0.74247 , 1120 0.00945 178.28 0.04261 0.75737 ) 1140 0.01168 181.88 0.04576 0.77260 1160 0.01430 185.55 0.04892 0.78818 . 1180 0.01737 189.31 0.05211 0.80420 1200 0.02100 193.19 0.05534 0.82075 1220 0.02524 197.18 0.05862 0,83790 1240 0.03013 201.31 0.06194 0.85569 1260 0.03575 205.58 0.06533 0.87424 1280 0.04221 210.02 0.06880 0.89366 1300 0.04959 214.64 0.07236 0.91405 1320 0.05795 219.46 0.07601 0.93550 1340 0.06738 224.49 0.07976 0.95814 1360 0.07801 229.76 0,08364 0.98213 1380 0.08993 235,29 0.08764 1.0075 1400 0.10318 241.08 0.09178 1.0346 1420 0.11788 247.16 0.09607 1.0633 1440 0.13412 253.55 0.10050 1.0940 1460 0.15197 260,26 0.10510 1.1266 1480 0.17151 267.31 0.10986 1.1614 1500 0.19276 274.70 0.11479 1.1985 . 1520 0.21576 282,44 0.11988 1.2379 1540 0.24050 290.53 0.12513 1.2797 1560 0.26699 298.96 0.13054 1.3240 - 1580 0,29515 307.73 0.13609 1.3708 1600 0.32485 316.80 0.14176 1.4200 1620 0.35597 326.16 0.14753 1.4715 1640 0.38830 335.76 0.15339 1.5252 Table 3 (continued) Weight Fraction 16 Temperature Enthalpy Entropy Specific Volume (°R) of AICI, (Btu/1b) [Brutb= 1. o)1) (73 /1b) At o Pressure of 60 psia 1660 0.42164 345.56 0.15929 1.5809 1680 0.45570 355.51 0.16521 1.6382 1700 0.49016 365.53 0.171n 1.6970 1720 0.52471 375.57 0.17695 1.7567 1740 0.55899 385.56 0.18269 1.8171 1760 0.59269 395.44 0.18830 1.8777 1780 0.62547 40513 0.19374 1.9382 1800 0.65706 414,58 0.19899 1.9981 1820 0.68721 423.75 0.20403 2.0570 1840 0.71573 432.59 0.20883 2.1148 1860 0.74248 441,07 0.21340 2171 1880 0.76737 44919 0.21771 2.2258 1900 0.79036 456.92 0.22178 2.2787 1920 0.81146 464,28 0.22562 2,3298 1940 0.83070 A71.27 0.22922 2.3791 1960 0.84818 477.91 0.23261 2.4266 1980 0.86397 484,21 0.23579 2.4723 2000 0.87819 490.19 0.23878 2.5163 At a Pressure of 100 psio 900 0.00039 141.82 0.00301 0.36188 920 0.00054 145.00 0.00647 0.36998 940 0.00074 148,19 0.00986 0.37809 960 0.00099 151.39 0.01320 0.38624 980 0.00132 154.61 0.01648 0.39441 1000 0.00174 157.84 0.01971 0.40263 1020 0.00224 161.10 0.02290 0.41090 1040 0.00291 164.38 0.02605 0.41923 1060 0.00371 167.69 0.02918 0.42763 1080 10.00470 171.03 0.03228 0.43613 1100 0.00589 174.42 0.03536 0.44473 1120 0.00732 177.86 0.03842 0.45346 1140 0.00904 181.35 0.04149 0.46234 1160 0.01107 184.90 0.04455 0.47140 1180 0.01346 188.53 0.04763 0.48067 1200 0.01627 192.24 0.05072 0.49017 1220 0.01955 196.05 0.05383 0.49994 1240 0.02334 199.95 0.05698 0.51003 1260 0.02770" 203.97 0.06018 0.52047 1280 0.0327¢ 208.12 0.06342 0.53130 1300 0.03843 212.41 0.06672 0.54259 1320 0.04491 216.86 0.07009 0.55438 1340 0.05225 221.47 0.07353 0.56673 1360 0.06051 226.27 0.07706 0.57970 1380 0.06976 231.26 0.08068 0.59336 Table 3 (continued) Temperature Weight Fraction Enthalpy Entropy Specific Volume °R) of AICI, {(Btu/Ib) [Btustb=1.(%R)~ 1] (53 /1b) At a Pressure of 100 psia 1400 0.08009 236.47 0.08440 0.60777 1420 0.09156 241.91 0.08823 0.62301 1440 0.10426 247.60 0.09218 0.63913 1460 0.11827 253.54 0.09625 0.65623 1480 0.13363 259.76 0.10045 0.67436 1500 0.15043 266.26 0.10478 0.69359 1520 0.16870 273.05 0.10925 0.71401 1540 0.18849 280.15 0.11386 0.73565 1560 0.20982 287.56 0.11861 0,75858 1580 0.23270 295.27 0.12349 0.78284 1600 0.25711 303.29 0.12850 0.80844 1620 0.28299 311.60 0.13363 0.83540 1640 0.31029 320.20 0.13887 0.86370 1660 0.33888 329.05 0.14421 0.89331 1680 0.36862 338.14 0.14961 0.92416 1700 0.39935 347.42 0.15507 0.95616 1720 0.43085 356.85 0.16056 0.98919 1740 0.46289 366.39 0.16604 1.0230 1760 0.49520 375.99 0.17149 1.0577 1780 0.52752 385.59 0.17689 1.0928 1800 0.55%956 395.13 0.18219 1.1283 1820 0.59106 404.56 0.18737 1,1639 1840 0.62176 413.84 0.19241 1.1993 1860 0.65141 422.90 0.19729 1.2346 1880 0.67984 431.72 0.20198 1.2693 1900 0.70686 440.26 0.20647 1.3034 1920 0.73235 448.50 0.21076 1.3368 1940 0.75624 456,42 0.21484 1.3694 1960 0.77849 464.00 0.21871 1.4010 1980 0.79907 471,26 0.22238 1.4317 2000 0.81802 478.19 0.22584 1.4614 At o Pressure of 150 psia 200 0.00032 141.81 0.00600 0.24123 920 0.00044 144,98 0.00344 0.24662 940 0.00060 148.17 0.00683 0.25203 960 0.00081 151.36 0.01015 0.25744 980 0.00108 154,56 0.01342 0.26288 1000 0.00142 157.78 0.01664 0.26833 1020 0.00184 161.01 0.01981 0.27382 1040 0.00238 164.27 0.02295 0.27933 1060 0.00303 167.55 0.02604 0.28489 1080 0.00383 170.86 0.02910 0.29050 1100 0.00481 174.21 0.03215 0.29617 1120 0.00598 177.59 0.03517 0.30190 17 Table 3 (continued) Temperature Weight Fraction Enthalpy Entropy Specific Yolume (R) of AICI, (Btu/Ib) [Btu-tb™ 1 (R)™ ] (#3/1b) At a Pressure of 150 psia 1140 0.00738 181.02 0.03817 0.30772 1160 0.00%204 184.50 0.04117 0.31364 1180 0.01099 188.04 0.04418 0.31966 1200 0.01328 191.65 0.04718 0.32582 1220 0.01596 195.33 0.05020 0.33212 1240 0.01906 199.10 0.05324 0.33859 1260 0.02262 202.96 0.05630 0.34526 1280 0.02671 206.92 0.05940 0.35214 1300 0.03138 211.01 0.06254 0.35927 1320 0.03668 215.21 0.06573 0.36668 1340 0.042468 219.56 0.06897 0.37438 1360 0.04943 224.06 0.07228 0.38243 1380 0.05700 228.72 0.07566 0.39086 1400 0.06546 233.56 0.07911 0.39969 1420 0.07487 238.58 0.08265 0.40898 1440 0.08529 243.81 0.08628 0.41876 1460 0.09679 249,26 0.09001 0.42908 1480 0.10944 254,93 0.09385 0.43997 1500 0.12329 260.84 0.09779 0.45149 1520 0.13840 267.01 0.10184 0.46366 1540 0.15482 273.43 0.10602 0.47654 1560 0.17259 280.13 0.11031 0.49016 1580 0.19174 287.10 0.11472 0.50455 1600 0.21228 294.35 0.11925 0.51974 1620 0.23421 301.87 0.12389 0.53576 1640 0.25751 309.67 0.12865 0.55261 1660 0.28214 317.73 0.13351 0.57031 1680 0.30804 326.05 0.13846 0.58883 1700 0.33510 334.60 0.14349 0.60817 1720 0.36320 343.36 0.14858 0.62828 1740 0.39221 352.29 0.15371 0.64911 1760 0.42194 361.37 0.15887 0.67059 1780 0.45220 370.56 0.16403 0.69264 1800 0.48277 379.81 0.16917 0.71517 1820 0.51342 389.07 0.17426 0.73806 1840 0.54391 398.31 0.17928 0.76121 1860 0.57402 407.46 0.18420 0.78449 1880 0.60352 416.50 0.18901 0.80778 1900 0.63219 425.37 0.19368 0.83097 1920 0.65985 434.04 0.19819 0.85395 1940 0.68635 442,47 0.20254 0.87662 1960 0.71155 450.65 0.20671 0.89890 1980 0.73537 458.55 0.21070 0.92071 2000 0.75774 466.17 0.21451 0.94200 18 (ref 15) are listed in Table 4. Aluminum chloride is stable on a free-energy basis relative to these pure container materials. |f, however, the products of a possible corrosion reaction are gaseous or form a solid or liquid solution and if a mechanism exists for the removal of the reaction products from the region of the reaction, a corrosion reaction might proceed. two positive valence states, Unfortunately aluminum exists in The chlorides AICI and AICl; are both gaseous in the temperature range of interest. Table 4. Free Energies of Formation of Aluminum Chloride and the Chlorides of Some Possible Container Materials Free Energy of Formaiion Metal {kcal per mole of CI) Chloeride At 500%K At 1000% AlCl, _48(g) —46(z) C:r('ll3 -35 --26 CrC12 ~40 -32 FE;C‘3 -23 -21 FeC|2 ~33 -27 NiCl2 -27 —-18 AICH =22g) -32(g) M0C|2 -15 -8 M0C|3 - 14 ) MoC|4 -12 ~7 MoCls ~10 -7 MoCl6 -7 -3 As an illustration of the possible corrosion behavior, the corrosion of an alloy containing chromium and nickel in a system in which gaseous aluminum chloride is circulated at temperatures in the range 500 to 1000°K is discussed here. The most likely corrosion reactions involving chremium are: Reaction A ZAICI,(g) + Cr &= CrCl,(s) + Al AF® gt 500°K = +16 kcal AF®at 1000°K = 428 kcal Reaction B AlClB(g) + Cr == AlCI(g) + CrCl{s) AFé at 500°K = +42 keal AF® at 1000°K = +42 keal Reaction C 3AICHg) == 2Al + AICI {2) AF® at 500°K = ~78 kcal AF®at 1000 %K = ~42 kcal The equilibrium constant, K, for reaction A is 2/3 “al dCrCtz K, = p~NF/RT _ T {19) p2/3 ' AlClB Cr = 10~7 at 500°K = 16-%-1 at 1000°K If pure aluminum is produced from the reaction of pure chromium and AICI, at a pressure of 1 atm, . . ~-6.1 o the activity of CrCl,, aCrCIQ’ is 10 at 1000°K and 10~7 at 500°K. The partial pressure of CrCl, under these conditions, P, , may be calculated from the relation 2 0 P = q P , (20) CrCI2 CrCI2 CrCi2 0 where PCrC|2 solid, which may be calculated from the relation ~14,000 is the vapor pressure of the pure 1 log Po crcl, (atm) = ~ 0.62 log T - -~ 0.00058T +12.26 . (21) The vapor pressure Pg is 10418 or 6.6 x 1075 rCl, atm ot 1000°K and 10~ '77% or 2 x 10~'8 atmat 500°K. The calculated partial pressures of CrCl, under the stated conditions are then 5.3 x jo-1 atm at 1000°K and 2 x 10725 atm at 500°K. In a system in which aluminum chloride gas was being 154, Glassner, The Thermochemical Pr%perzz'es of the (le(}z'des, Fluorides, and Chlorides to 25007 K, ANL-5750 57). 19 circulated, if reaction A were the only significant one, it would take a minimum of 2 x 109 moles of aluminum chloride gas to move 1 mole of CrCl from the hot zone and deposit it as solid CrC|2 in the cold zone. The fact that the aluminum metal produced in reaction A might form a solid solution with the metal wall in the reaction zone would increase the initial portial pressure and transport of CrCl,. After an initial deposit of aluminum metal had formed on the surface, the reaction would yield a smaller partial pressure of CrCl,, with diffusion of aluminum into the metal in the hot zone being one controlling factor for this partial pressure if reaction A were im- portant. Not only is the initial activity of chro- mium in an alloy lower than that of the pure metal, but the depletion of the surface chromium concen- tration would further lower the activity of chromium at the surface and, hence, lower the maximum partial pressure of CrCl, in the circulating gas at the hot end. This would lead to a smaller transport of CrCl, from the hot to the cold zone. The chromium concentration on the reaction surface and, hence, the corrosion rate, would then be controlled by the diffusion of chromium to the surface in the hot zone. This diffusion would be a second controlling factor if reaction A were important. The equilibrium constant for reaction B is PAIClaCrCi2 K = o-NF/RT _ B - P a Alciy“ce PAICIPCrCI2 = (22) p pe A|c13“cr crCl, = 10— 184 4t 500°K =10~ 72 43¢ 1000°K For pure chromium exposed to aluminum chloride at a pressure of 1 atm, p =]O“9'2X]0“4°]8:’:10"]3'4 e AlCH CrCI2 at 1000°K and _ _ -6.7 ~7 PAICi‘PCrCI2‘m or 2 x 10 20 This pertial pressure is higher than that which would be present above a chromium-containing alloy in which the activity of the chromium was lower than the activity of pure chromium metal. The partial pressure of Cr(:l2 from reaction B is higher than that from reaction A. Reaction B should be, therefore, the important corrosion reaction and should result in the transport, at the very most, of about 2 x 107 mole of chromiym per mole of circulating gas. At the low-tempera- ture zone, CrCl, will initially deposit as the solid, AICI will disproportionate according to reaction C, and a small concentration of aluminum will deposit on the surface of the alloy. After a small activity of aluminum is built up in the metal, the reaction at the low-temperature zone should be the reverse of reaction B, with chromium metal being deposited on the walls, At the hot zone, after the surface chromium has been depleted, the reaction will be limited by the diffusion of chro- mium from the interior of the metal to the surface. If reaction B is important, this diffusion of chro- mium fo the surface at the hot zone will probably be the rate-controlling step in the transport of chromium metal from the hot to the cold zone. l.owering the temperature of the hot zone would decrease the rate of corrosion, mainly by lowering the diffusion rate of chromium. The formation of an adherent nonmetallic film on the surface that is not attacked by aluminum chloride would also decrease the corrosion rate, The corrosion of nickel would be much less severe, The reactions significant for nickel corrosion are: Reaction D %AICH,(g) + Ni =2 NiCl,(s) + %Al AF® at 500°K = +42 kcal AF° at 1000°K = +56 keal Reaction E AlCls(g) + Ni &= AICI(g) + NiCl,{s) AF° at 500°K = +68 kcal AF®at 1000°K = + 70 kcal The equilibrium constants for reactions D and E are: 2/3 Al aNiClz K == DE/RT _ D g p2/3 NIt AICH, 2/3 Sy PNiCI2 ——— () 2/3 p0 aNiPA|CI3INiC12 = 10~ 18-4 4 500°K = 10~ 12:2 4 1000°K , PAICl“NiClz K :e-AF/RTz ] PA!C!3“Ni P P AlICITNICH, —- (24) 0 aNipAlC!BPNiClz = 10~29-8 4 500°K = 10— 153 44 1000°K The vapor pressure of pure NiCl,, PgiClzf may be calculated from the equation’ 13,300 log PgiClz (atm) = - 2.68log T +19.00 . (25) At 1000°K, Pg‘CI is 10234 or 4.6 x 102 atm 12 and at 500°K it is 10- 1483 or 1.5 x 10~ 15 atm. At the high-temperature zone, reaction E leads to a higher partial pressure of NiCl, than does reaction D. For the corrosion of pure nickel, P ! - P NiCl, — © AlICI 2 - (10=15-3 , 10-2:3) /2 =10-8-8 o 1.6 x 1077 atm At the low-temperature zone, the reverse of re- action E will probakly take place, and nickel metal will deposit on the surface. The limiting factoer in the corrosion of nickel from an alloy composed principally of nickel would be the total volume of gas passing over the surface. One mole of nickel would be transperted per 6 x 10% moles of gus at 1 otm passing the surface at 1000°K. One mole of AICH, transports roughly 20 keal of heat in going from 1000 to 500°K, so about 1 mole of nicke! would be transported per 1.2 x 1010 keal, 1.4 x 107 kwhr, or about 600 Mwd of heat. The transport corrosion of iron and molybdenum as minor constituents of an alloy should be less than that of chromium, In conclusion, corrosion of an alloy composed mainly of nickel and contoining some chromium might not be negligible for long-term operation of a system circulating gaseous aluminum chloride at temperatures in the range 500 and T1000°K, but the corrosion would be small enough for short-term operation of such a system. The corrosion rate could be decreased considerably by operating with the hot zone of the loop at temperatures lower than the 1000°K for which these calculations were made or by the formation of an oxide coating on the surface of the metal. The estimated values of the thermal conductivity, heat capacity, and viscosity indicate that aluminum chleride may be a unique gaseous heat exchange medium that requires very low pumping power. It should be emphasized that these cre crude estimates based on a limited amount of data of varying degrees of reliability. Although a conscious attempt has been made to moke these estimates conservative, some of the estimates should be checked experimentally. ENGINEERING PROBLEMS OF SOME TYPICAL APPLICATIONS Where cluminum chloride vapor is used as « working fluid in a thermodynamic cycle or as a heat transfer medium, the pressures and tempera- tures must be carefully chosen to exploit to the fullest the extra performance obtainable from dissociation. MNormally a temperature range will be defined by the structural strength of the metals in the system or by other considerations, such as corrosion, so that the only variable available to the designer will be the pressure. This meons that the pressure level must be chosen with care to give the best over-all system design. It is likely that it will be necessary to compromise the design of other components if the fullest benefits are to be derived from the use of aluminum chloride. Aluminum Chloride as a Heat Transfer Medium A typical applicetion for which aluminum chloride may have promise is as an intermediate heat 21 transfer fluid between the fluoride fuel of a molten- salt-fueled reactor and the steam generator. The use of a gas rather than a liquid in the intermediate loop would facilitate removal of the heat transfer medium; it would not be necessary to design the system to avoid the presence of low spots which would present difficult drainage or scavenge problems. It would make possible the placing of flanged joints in cool zones at the top of the system and outside of the heat exchanger pressure envelope so that leaks of the molten fuel into the aluminum chloride would be contained within the pressure envelope. The pressure required, namely, 20 to 60 psi in the aluminum chloride, would present no serious structural problems in the design of the containing vessel. From Fig. 4, which is a plot of data obtained from Eq. (7), it is evident thot there would be no solid aluminum chloride precipitated at the temperatures and pressures prevailing in a molten-salt-fueled re- actor. . Aluminum chloride would have the ad- vantage as a heat transfer fluid thot it would UNCLASSIFIED ORNL-LR~DWG 39597 e . . . 1 | S — © SOLID PHASE l PRESSURE (psia} i wf— - ——T | 1 ‘ l“ 800 4000 1200 1400 1600 1800 2000 TEMPERATURE (°R) Fig. 4. Ges-5clid Equilibriom Diagrem for Aluminum Chloride. 22 be chemically inert relative to either the molten salt or water. This would make it desirable from the hazards standpoint and would give o system relatively insensitive to leaks between any two sets of fluid; that is, a small leak from one system into another would not lead to the formation of a set of deposits which would be very difficult to remove. |t would be necessary, of course, to make the steam generator, as well as the fuel~ to—aluminum chloride heat exchanger, of arelatively expensive high-nickel-content alloy. The principal disadvantage of this arrangement is that it would require a larger amount of heat transfer surface area and a higher pumping power than would be the case for an inert molten salt, for example. However, it would have a major in that there would be no freezing problem in the intermediate heat exchanger circuit. The freezing problem presents exceedingly dif- ficult design problems if a fluid such as sodium or NaK is employed as the intermediate heat transfer medium. advantage The temperature range for such an application is lower than is desirable in that the heat transfer surfaces for the molten salt would be at about 1100 to 1200°F, while those inthe steam generator would be at 700 to T000°F. As may be seen in Fig. 1, this temperature range is below that which gives the maximum obtainable average effective specific heat if the pressure is maintained high enough (30 to 100 psi) to keep pumping losses to acceptable levels, Aluminum Chioride Vapor in a Gas-Turbine Cycle The features of a gas-turbine cycle utilizing aluminum chloride deserve special attention. The cycle contemplated is indicated schematically in Fig. 5. The pressures and temperatures should be chosen so that the gas will be mostly in the form of A|2CI(, during compression, while during the expansion process it will be mostly AlCI,. This, in effect, will cut the compression work roughly in half and thus produce a marked improve- The naoture of this effect can be visualized readily by examining the ment in cycle efficiency. P-V diagrams of Fig. 6, which compare similar ideal gas-turbine cycles for helium, aluminum It should be remembered that the work involved in each compression or ex- chloride, and water. pansion process is directly proportional to the area of the P-V diagram, and the net work is UNCLASSIFIED ORNL~~LR—-DWG 39538 I GENERATOR I REACTCOR FRESSURE {psia} PRESSURE {psiaj URE {psial TUR Fig. 5. Aluminum Chloride Gas-Turbine Cycle. COMPRESSOR DM OO0 RANKINE CYCLE (H,0) BRAYTON CYCLE (Ai,Clg— AICly) proportional to the net area for the cycle. The Rankine cycle utilizing water vapor was included in Fig. 6 to show that the proposed aluminum chloride cycle is between a gas-turbine (or Brayton) cycle utilizing helivm and a Rankine cycle utilizing water in its requirements for work input during the compression process. The diagrams of Fig. 6 were prepared for ideal cycles with no allowances for losses. The most important of these losses are associaoted with the efficiencies of the compressor and the turbine, which are likely to be of the order of 85%. This means that, with an 85% efficient compressor, the ideal work input will be 85% of the actual work input, while the actual work output of the turbine will be only 85% of the ideal. in addition, pressure drops between the compressor and the turbine will UNCLASSIFIED CRNL--LR--UWG 34577R BRAYTON CYCLE (He} S 1 sl 4 T - 0 W ; o < | L L ...... I oo Ira | - 2 o IDEAL WORK INPUT =6.43 Bfu/lb ffu) IDEAL W PUT =251 Btu/lp o ICEAL WORK INPUT =477 Btu/ip 4- A « I R e | o o [T T a I - a ‘ | | | f i o ‘ E | ] | \ \ \ Y {IDEAL WORK QUTPRUT =6338tu/lb IDEAL WORK GQUTPUT = 62.7 Btu/lb ~ i oo 5 Moo b el Sl N 2 B | o o L L - B o pee-eeee-eer- e o 2 > | oy [9p] & @ IDEAL WORK GUTPUT = 604 Bitu/ib B & N R S s x L | B e e N—— \_M i | \ I | ] J IDZAL NET WORK =832.6 Btu /b INEAL NET WORK = 37.6 Btu/lb | T L L] L] sl ] n Yy A | & L { L | e o ... e - [ e e e b ! D = . | | oy o) . . 0 ‘ A IDEAL NET WORK =1Z7 Btu/lp Lt L o @ | | [ 4 T ‘ ,,,,,,,,,,,,,,,, — o b e | ] VOLUME (F13/ 1) Fig. 6. VOLUME (f13/10) P-V Diagrams for Typical !deal Thermodynamic Cycles. 23 also cause major losses in net output from the cycle. The nature of these effects can be seen readily in Fig. 7. It should be emphasized that the shaded portions of these diagrams are merely propertional to the losses they represent and thot the actual paths shown. A rough allowance for these pressure of the processes cannot be losses can be made by using lower values for the turbine and compressor efficiencies, for example, 80% in each case. If allowances are made for these losses to obtain the actual net outputs for the cycles of Fig. 6, the diagrams of Fig. 8result. The relatively large work input required for the compression process of the Brayton cycle makes the cycle efficiency very sensitive to compressor inlet temperature because the compression work in- creases rapidly with temperature. As a result, the net work output and over-all cycle efficiency of the Brayton cycle drop off so rapidly with in- creasing temperature at the compressor inlet that, for any practicable plant, the compressor inlet UNCLASSIFIED ORNL~-LR-DWG 34727 T T 80 PRESSURE L 0SS THROUGH HEATER I e ST i | TURBINE INLET TEMPERATURE = ’ 4500"1;—- 60 | b R —NET EFFECTIVE AREA | > —EDDY LOSSES IN TURBINE 40 Lo b 20 }EDDY LOSSESIN — COMPRESSOR = . - e | | PRESSURE LOSS L { J THROUGH COOLER X 0 s ! 1 i s} ? [ N ! f o —~PRESSURE LOSS THROUGH HEATER O_ BO - o e '*" I ‘ TURBINE INLET TEMPERATURE = 1200°F B0 [ B e | NET EFFECTIVE AREA ‘ 20 —EDDY LOSSES IN TURBINE EDOY LOSSES IN! 20 — COMPRESSOR - THROUGH COOLER | o 4 8 12 16 20 24 28 0 SPECIFIC VOLUME (ft7Ib) Fig. 7. P-V Diagrams for ldeal Gas Turbine Air Cycles with Cross-Hoatched Areas to Indicate the Magni- tude of the Principal Losses. 24 temperature must be held below 150°F if con- ventional working fluids are used. At the same time, the turbine inlet temperature must be at least 1200°F, and preferably should be above 1400°F if there is to be an appreciable positive net area for the P-V diagram. The wunusual properties of aluminum chloride make it possible to go to higher compressor inlet temperatures than with other fluids. The effects of variations in both the compressor inlet tempera- ture and the compressor pressure ratio are indicated in Fig. 9 for a turbine inlet temperature of 1540°F, While this temperature is high by steam power plant standards, the much lower pressures in the aluminum chloride system reduce stresses suf- ficiently to compensate for most of the temperature difference. In any event, it is necessary to go to peak temperatures in this range to take full od- vantage of the unusual properties of the aluminum chloride. Itisevident from Fig. 9 that the aluminum chloride vapor cycle should be designed for a compressor inlet temperature of around 540 to 640°F and a pressure ratio of 20 to 40. Further lowering of the compressor inlet temperature will do little to enhance efficiency, since at 540°F most of the gas is in the dimer state already. A point of interest is that it was found in the cycle analysis that during the compression and expansion processes there was little change in the percentage of the gas dissociated. This will simplify the design of compressors and turbines for such an application. The hect transfer coefficient for the aluminum chloride is sufficiently high for the high-pressure portion of the cycle, and therefore good heat transfer could be cobtained in a reactor core. |In the cooler, however, the heat transfer performance of the aluminum chloride would be poor, and a large surface area would be required. The poor heat transfer coefficient of aluminum chloride in the cocler stems from the fact that the pressure at the turbine outlet would be only approximately 1/10 otm, and this would give a low Reynolds number. The pressure ahead of the turbine, on the other hand, would be 20 to 40 times greater, which would give heat transfer coefficients corre- spondingly higher. Binary Vapor Cycle Applications If aluminum chloride were used as a reactor coclant or as an intermediate heat transfer fluid RANKINE CYCLE {H,0) BRAYTON CYCLE [A1LCIg-AICIg) UNCLASSIFIED ORNL~LR ~-DWG 34578R BRAYTCN CYCLE (He) ACTUAL WORK INPUT = 12.88 Btu/1h | | ACTUAL WORK INPUT = 31.2 Btu/lb — L ) I —~L W] — R ] 53] ! Lt @ L el L o D -1 T T T = o s oy wy h o+ U} w i w e o o - ~ - 4 - — l .. / ; | _J - > i ] J b r i I 7 it ACTUAL WORK OUTPUT = 51¢ Biu/ib = 50.2 Btu/!b 77 3 | t /, - ol M __fiq ] - . — h_J LGN e y & | & 2 7 2 & I N - e Z 2 2 > : - | o) o o ; E ’ IR L|J‘ J L i | o _ R & 3§ ACTUALWORK OUTPUT = 493 Biu/lp | < | ] o | T T b ACTUAL NET WORK =498 Btu/Ib 19 8tu/lb L ACTUAL NET WORK =— 104 Btu/Ib — T A o I —_ Lo I [V 2 - = o o o . L oW L L] el sl ] o D -2 o W 3 ) ) o )y Ll ul i [ vy i ' a. - a— A Q. =1 T T N S———— i | . ‘| i VOLUME (£13/1b) Fig. 8. VOLUME (1 ¥1p) VOLUME (1 3/1n) P-¥ Diagrams for Typical {deal Thermodynamic Cycles with Cross-Hatched Areas to Represent the l.osses Entailed by Compressor and Turbine Efficiencies of 80%. for a molten-salt-fueled reactor, it appears that a binary vapor cycle employing aluminum chloride in the high-temperature portion and water vapor in the lower-temperature region ought to be con- sidered. Such a cycle would resemble in many ways the binary mercury vapor~steam cycle which has been used in a number of U.S, power plants. It would have the advantage that it would permit operation at high temperctures (which would be advantogeous from the thermodynamic standpeint) while avoiding the expense associated with the high pressures characteristic of high-temperature steom cycles. While there are a host of different combinations of conditions that might be employed, a typical case is presented in Table 5. The aluminum chloride would be expanded through a turbine similar to that described above. The cooler for the aluminum chloride would also serve as the boiler and superheater for the steam sys- tem. It may be seen from Table 5 that this system gives a very much higher over-all thermal efficiency than is obtainable from the gas-turbine cycle alone. A corresponding steam system designed for a pressure of 2400 psi and a peak temperature out of the superheater of 1050°F would give an over-all thermal efficiency of about 38%, some- what less than the efficiency that the typical binary vapor cycle chosen would attain. 25 UNCLASSIFIED ORNL—LR~DWG 39601 14 r T I TURBINE INLET TEMPERATURE = 2000°R TURBINE INLET PRESSURE = 60 psia COMPONENT EFFICIENCIES COMPRESSOR 80% 12y TURBINE 80 % GENERATOR 90% COMPRESSOR INLET 10 #—‘ __________________ __ TEMPERATURE °oR i grsas o LLJ O Z 8 - b S / & 1200°R o] ‘fi'-n_._‘_._.‘- - | a Y AN 4 o o ! w ——— O 20 30 40 PRESSURE RATIO Fig. 9. Cycle Efficiency vs Pressure Ratio for AlCl,. CONCLUSIONS Thermodynamic data have been prepared and are presented in the form of tables and charts to facilitate engineering calculations on systems employing aluminum chloride vapor either as a heat transfer medium or as the working fluid in a thermodynamic cycle. A number of typical appli- cations have been considered, but in none of these 26 has the aluminum chloride shown outstanding advantages over more conventional media. How- ever, it is believed that for some special appli- cations it may well prove to have some outstanding advantages where the characteristics of the other system components are such as to make it possible to exploit to the fullest the unique characteristics of aluminum chloride. Table 5, Binary Yaper Cycle ldeal mass rotio = 0.18487 Ib of water per Ib of aluminum chloride Actual mass ratio = 0.19585 lb of water per Ib of aluminum chleride ldeal cycle efficiency = 53.2% Actual cycle efficiency = 41.4% Specific Weight Fraction Condition Temp;rafure Enthalpy En?ropzf Presmsure Volume Dissociated or ( F) (B?IJ/“)) (BfU/Of‘) (pSlG) (1&3/”\_)) S‘hecm QUG“"Y Aluminum Chloride Compre ssor inlet 440 142 0.02530 5 7.2476 0.00176 Compressor outlet 570 164 0.02530 100 0.41506 0.00259 {isentropic) Compressor outlet 615 169.5 0.0311 100 0.4344 0.00447 (80% eHiciency) Turbine inlet 1540 478 0.22584 100 1.4614 0.818 Turbine outlet 1150 406 0.22584 5 23.07 0.781 (isentropic) Turbine outlet 175 420.4 0.2343 5 23.92 0.812 (80% efficiency) Steam™ Pump inlet 91.72 59.71 0.1147 0.7368 0.01611 Saturated liquid Fump outlet 91.72 66.14 0.1147 2400 0.01600 Compressed liquid (isentropic) Fump outlet 91.72 72.57 0.1243 2400 0.01600 Compressed liquid {(50% efficiency) Tuwbine inlet 1050 1494 1.5554 2400 0.3373 Superheated vapor Turbine outlet 91.72 855 1.5554 0.7368 339.5 0.763 (isentropic) Turbine outlet 21.72 983 1.790 0.7368 394.2 0.884 {80% efficiency) *The bases for enthalpy and entropy of aluminum chloride and steam are not the same. Hence comparisen of the absolute values of these properties between the two fluids is meaningless. 27 ORNL-2677 Reactors~Power TiD-4500 (14th ed.) INTERNAL DISTRIBUTION 1. L. G. Alexander 58. R.S. Livingston 2. D. S. Billington 59. H. G. MacPherson 3. M. Blonder 60. W. D. Manly 4, F. F. Blankenship 61. J. R. McNally 5. E. P. Blizard 62. K. Z. Morgan 6. A. L. Boch 63. J. P. Murray (Y-12) 7. C. J. Borkowski 64. M. L. Nelson 8. G. E. Boyd 65. R. F. Newton 9. M. A, Bredig 66. A. M. Perry 10. E. J. Breeding 67. P. M. Reyling 11. R. B. Briggs 68. G. Samuels 12. C. E. Center (K-25) 6%2. H. W. Savage 13. R. A. Charpie 70. A. W. Savolainen 14. F. L. Culler 71. H. E. Seagren 15. L. B, Emlet (K-25) 72. E. D. Shipley 16-17. L. G. Epel 73. J. R, Simmons 18. W. K. Ergen 74. M. J. Skinner 19. D. E. Ferguson 75. A. H. Snell 20-45. A. P. Fraas 76. J. A. Swartout 46. J. H. Frye, Jr. 77. E. H. Taylor 47. W. R. Grimes 78. A. M. Weinberg 48. E. Guth 79. C. E. Winters 49, C. S. Harrill 80. Biology Library 50. H. W. Hoffman 81. Health Physics Library 51. A. Hollaender 82. Reactor Experimental 52. A.S. Householder Engineering Library 53. W. H. Jordan 83-84. Central Research Library 54. G. W. Keilholtz 85-104. Laboratory Records Department 55. C. P. Keim 105. Laboratory Records, ORNL R.C. 56. M. T. Kelley 106-110. CRNL -~ Y-12 Technical Library, 57. J. A, Lane Document Reference Section 111. 112. 113. 114. 115-696. EXTERNAL DISTRIBUTION W. C. Cooley, NASA, Washington F. E. Rom, NASA, Cleveland, Ohio W, D. Weatherford, Southwest Research Institute Division of Research and Development, AEC, ORO Given distribution as shown in TID-4500 (14th ed.) under Reactors-Power category {75 copies — OT3) 29