Thermodynamic Properties of Elements Their Oxides, Halides, Carbides and Nitrides

Bulletin 605 Bureau oF Mines THERMODYNAMIC PROPERTIES OF 65 ELEMENTS— THEIR OXIDES HALIDES CARBIDES AND NITRIDES By C. E. Wicks and F. E, Block UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON: 1963UNITED STATES DEPARTMENT OF THE INTERIOR Stewart L. Udall, Secretary BUREAU OF MINES Marling J. Ankeny, Director This publication has been cataloged as follows: Wicks, Charles E Thermodynamic properties of 65 elements—their oxides, halides, carbides, and nitrides, by C. E. Wicks and F. E. Block, Washington, U.S. Govt. Print. Off., 1963. (U.S. Bureau of Mines. Bulletin 605) 1. Thermochemistry. 2. Oxides. 3. Halides. 4. Carbides. 5. Nitrides. I. Block, Frank B., joint author. I. Title. (Series) ‘TN23.U4 no. 605 622.06173 US. Dept. of the Int, Library For sale by the Superintendent of Documents, U.S. Government Printing Otfice ‘Washington 25, D.C. Price $1.00Page Introduction . - 1 Part 2.—Heat content, heat-of-formation, and ‘Symbols and units 2} free-energy data—Continued Part 1—Thermodynamie functions and their Lead and its compounds. 3 Lithium and its eompounds- 3 Tiutetium and its compounds: 4 Magnesium and its compounds 5 Manganese and its compounds. Free energy. 7 Mercury and its compounds. Part 2.—Heat content, ‘Molybdenum and its compounds. free-energy data. = 10 Neodymium and its compounds. Aluminum nd its compoun 5 10 ‘Antimony and its compounds. eet Arsenic and its compounds. nt Barium and its compounds. 16 Beryllium and its compoun: 18 Bisinuth and its compounds. 20 Boron and its compounds, 22 Broming 24 Promethium and its compound Cadmium and its compounds * 24 Rhenium and its compounds. Calcium and its compounds. * 26 Samarium and ite compounds Carbon and its compounds. 28 Scandium and its compound Cerium and its compounds. * 32 Siifeon and its eompounds. Chior! - 383 Silver and its compounds. Chromium and its compound - 34 Sodium and its compounds Cobalt and its compounds. ¢ 38 Strontium and its compounds Columbium and its compounds © 40 ‘Tantalum and its compounds. 5 41 Terbium and its eompounds.. Dag D458 8 < 47 Titanium and its compounds: © 48 ‘Tungsten and its compounds: © 49 Uranium and its compounds. = 51 Vanadium and its compounds: < 82 Ytterbium and its compound ¢ 58 Yttrium and its compounds. "56 Zine and its compounds. 37 ireor < 62 References. ILLUSTRATIONS He 1. Aluminum, 2 Antimony 3. Arsenic. 4 5. Beryl 6 7 8 9. 10. 1 12, Chromium (aj. Praseody miu, SSRFSSSSSRISSE SEE Promethium, Titania (0 anu (0): ngsten Uranium (a) Uranium (6) CONTENTSTHERMODYNAMIC PROPERTIES OF 65 ELEMENTS—THEIR OXIDES, HALIDES, CARBIDES, AND NITRIDES' by C. E. Wicks? and F. E. Block* Introduction IHROUGH the utilization of two branches of scientific knowledge, extractive metallurgy has recently developed from an empirical art ‘to a more exact science. Improved techniques for evaluating physical and chemical properties of materials have provided better definition and control of operating variables. Also, chemical thermodynamics have provided the requisite fundamental information needed to evaluate optimum conditions for conducting processes. ‘The value of thermochemical calculations in extractive metallurgy is in evaluating heat requirements and optimum conditions for conducting # chemical process, Quantitative knowledge of thermodynamic values characteristic of elements and compounds is almost mandatory in the control and improvement of established extractive metallurgical processes, as well as for the development of new or modified processes. This Bureau of Mines bulletin was prepared to compile in readily usable form the heat content, heat-of-formation, and free-energy-of-formation data for 65 common elements and their respective oxides, halides, carbides, and nitrides. ‘The bulletin was prepared to encourage the application of thermo- dynamies in the metallurgical field; consequently, the values have been presented in a simple, readily usable form and several examples of their applications have been shown. The necessary theoretical basis of chemical thermodynamics is discussed in part 1 of this’ bulletin. It is assumed that the user will be at least ac- quainted with the fundamentals of chemical thermodynamics. Accordingly, all derivations of the various functions and their interrelations have been climinated, ‘These can be found in various textbooks. ‘This part contains the essential formulas necessary for applying fundamental data to process problems, with the accompanying examples included mainly to illustrate their applications, A survey of literature published through 1959 permitted assembly of all accepted measured and estimated thermodynamic values. ‘These values are included in part 2 of this bulletin, To satisfy individual needs, these data, have been presented in three separate forms: (1) Tables of heat content, 2 Edm anglnat A founy etary Mesmech Center, Bureau of Mine, Albany, 0 | Supervisory ehemieal engineer, Albus Metallurgy Resarch Center, Burcu Of Mines, Albany, Ores.2 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS heat of formation, and free energy of formation at various temperatures as well as values for’phase changes; (2) equations relating the variation of the thermodynamic functions with temperature; and (3) graphical plots of the variation of free energy of formation with temperature. The stable form of elements and compounds at the reference base temperature of 298.15° K. was used as the standard state. An effort was made to differentiate between established and estimated values. Parenthesized values within the tabular data, and dotted lines on the graphs indicate regions where estimations: were required. It is important to emphasize that thermochemistry deals with equilibrium conditions only, and thot many reactions are in practice subject to gversiding kinetic imitations, rather than free-enengy relationships. It, is impossible to evaluate or predict reaction rates from thermodynamic calculations. A simple parallel may be drawn from the fact that the knowledge of the amount of gasoline available to drive an automobile gives no indication of the length of time required to traverse a busy city. ‘The driving force causing a reaction to proceed and the ultimate state of the reacting system can be calculated from reliable data, but. the resistance to attainment is in- capable of prediction without additional kinetic information. SYMBOLS AND UNITS‘ a,b, ¢, 7, 8) Constants in various equations. AA, Op, On, Os Activity for reactants and products. A, By RS. Reactants and products in the general chemical reaction equation, Crystalline state of elements and compounds, Normal boiling point, ° K. Heat eapacity, calories per gram-mole per ° K. Electromotive force, volts, Entropy units, calories per gram-mole or atom per ° K. Free-energy change, calories per gram-mole or atom. Standard free-energy change, calories per gram-mole or atom. Faraday’s constant, calories pet volt equivalent. Heat content, calories per gram-mole or atom. Heat of fusion, calories per gram-mole or atom. Heat of reaction, calories per gram-mole or atom. Heat of formation at given temperature, calories per gram-mole or atom. Heat, of vaporization, calories per gram-mole or atom. Equilibrium constant. Normal melting point, ° K. ‘Number of electrical equivalents involved. Partial pressure, millimeters of mercury. . Heat exchanged between system and surroundings, calories. Gas constant, 1.987 calories per ° K. per gram-mole. Entropy, calories per gram-mole per ° K. ‘Absolute temperature, ° K. ‘Transition point {The folowing embols ace ud in the stations BoRalloe D—DeantpattionPART 1—THERMODYNAMIC FUNCTIONS AND THEIR APPLICATIONS A. knowledge of thermodynamic functions can provide an excellent guide in the control and improvement of established metallurgical processes. Screening programs based on thermodynamic calculations can also be used to indicate the most favorable approach to the development of new extractive metallurgical processes. Heat content, heat of reaction, and free energy of formation are the principle thermodynamic functions needed in evaluating heat balances and in predicting proposed chemical reactions. HEAT CONTENT Heat content is the basic thermodynamic function required for heat balances, as well as for many other useful chemical calculations. For a system undergoing an isobaric change, it can be shown from the first law of thermodynamics that AH=Q. This simply states that whenever a process is carried out under constant. pressure, the heat, absorbed or evolved by the system, Q, is equal to the change in the heat content of the system, AH. Since the heat content is a funetion only of the state of the system, the change in heat content that occurs during any process is independent of the path by which the particular process takes place. Accordingly, the change in heat content depends only on the initial and final states and the heat absorbed or evolved in a metallurgical process can be calculated from values of the heat content at the initial and final states. Because of the relative importance of this thermodynamic property, physical chemists and metallurgists have made relatively com- rehensive experimental measurements of the eat contents of pure substances in their various physical states. Since it is difficult to evaluate absolute heat content values, the quantities generally determined experimentally are changes in heat content above an arbitrarily chosen base temperature. The temperature 298° K., or 25° C., has been conventionally accepted as the base temperature for metallurgical thermochemistry. Pure elements in their stable form have been assigned a zero heat content at this temperature. The heat content of compounds in their stable state at 298° K. is equal to the heat of formation from their elements at this temperature. The change in heat content, (Hy—Hi), is referred to as the heat content of a substance above the reference base temperature. . Considerable effort has gone into compiling, simplifying, and systematizing values for the heat contents of elements and compounds. Changes in heat content with temperature for pure substances may be represented in graphs or tabulations, or by empirical equations A change in heat’ content with temperature is directly related to the heat capacity, C, of the substance by the equation: Hy—Hm= [CoA Since C, is normally expressed as C= at bT Her, the relationship for a given physical state becomes e-timgaats Perse Because a heat capacity relationship holds only for a given physical state, that is, solid, liquid, or gas, it is important that the specific relation ship be used only for the temperature range in which it is valid. | . ‘After a solid is heated to its melting point, additional heat must be supplied to melt it ‘The heat required for melting at constant pressure is equal to the increase in heat content and is known as the heat of fusion, AHy. An equal quantity of heat is liberated when the reverse operation, solidification, takes place; that is, Heat of fusion—hest of erystallization. Similar heat effects accompany other changes in physical states of substances, such as heat 84 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS of transformation and heat of vaporizati Values of heat effects accompanying changes in state vary with the temperature and pressure under which the change is earried out. Accord- ingly, values usually reported are those for the normal melting temperature, transition temperature, or boiling temperature at 1 atmosphere pressure (14.7 p.s.i.a.). ‘The empirical heat content relationship for a substance that undergoes phase changes in being heated from 208° K to some higher temperature can be represented by the equation: Hr—-Hm= foe CG MP C,(6)dT atte [2% csoarsainel ™, coer Obviously, the evaluation of heat content values by this empirical equation involves burdensome calculations. Fortunately, tables have been prepared in which heat’ content values at various temperatures are reported. Exhaustive compilations by Kelley (78-83),' Rossini (112), Brewer (6-9, 11, 12), Coughlin (24), and Stull (130) deserve particular mention. ‘The most frequent, use of heat content data, by the metallurgist is in determining the amount of heat evolved or absorbed when the temperature of a substance is changed during a process For such calculations, heat content data in tabular form require ‘only simple arithmetic interpolation to reveal the heat content at any temperature. Heat evolved or absorbed during fa temperature change under constant. pressure is found simply as the difference between the heat contents at the two temperatures. Exampte 1: Caleulate the heat required to raise 1 gram-mole of calcium dichloride from 400° K. to 1,200° K. using values from tabulations in part 2 of this bulletin. (Calcium dichloride melts at 1,055° K.) At 1,200° K., Hs» — Han=24,840 ealories per mole. At 400° K., Hys—Hw=1,850 calories per mole. AH=H, 90~ Hyo=22,990 ealories per mole. ‘The solution of this example, using the empir- ieal equation, would require solving AHH Hom fp Caled + atu f Cy Dar oss icp (1718+3.04%10- 70.00 1057-4 +-07004 f'SPoz0an lalicied pumbers tn parentheses rler to cftationt in the lst of referenoor at the end ofthis reper, HEAT OF REACTION AND HEAT OF FORMATION Chemical reactions are accompanied by changes in energy distribution between the reacting systom and its environment. ‘These are indicated by the evolution or absorption of heat, Since’ system generally becomes more stable as its heat content decreases, the reaction will normally proceed toward the state having the lower heat content. This results in a negative value for the heat of reaction, corresponding to an evolution of heat during the reaction, ‘When heat is generated, a reaction is referred to as exothermic, and when heat is absorbed, it is considered endothermic. Exothermic reactions are self-sustaining, once initiated, while endothermic reactions require additional energy if they are to continue. By simple additions and/or subtractions, the heat, involved in any chemical reaction may be determined. Consider the equation for a general reaction: aA+bB- +38. ‘The heat of reaction, AH, can be calculated by subtracting the algebraic sum of the heat content of the reactants from the algebraic sum of the heat content of the products. Total heat content, of each substance participating will be equal to the product of its heat content at a given temperature and the number of atoms or moles participating in the reaction. For the above general reaction, this calculation can be represented empirically: AH, =[r(Hx) +8(He)]—[a(H,) + 0(H9)) Exampte 2: Determine the heat of reaction for the reduction, of dichromium trioxide, by calcium at (1) 298° K. and also at (2) 500° CrOy+3 Ca +3 Ca0+2 Cr 1. Heat of reaction at 298° K. 272,650 calories per mole. 0 ealories per atom. ~ 151,790 ealories per mole. ‘afiey=0 ealories per atom. SH =(3(Howo) + 2(Hor)]— (Heros) +3 (Hew) [3(— 151,790) + 2(0)]—[(— 272,650) +3(0)] 's55,370++272,050 1827720 calories per mole of Cr,0s. . Heat of reaction at 500° K.—This can be evaluated by using the heat content, Hy, of each reaction participant, as will now be illustrated, or by simple addition of heats of formation as illustrated in example 3 Reactior Heros‘THERMODYNAMIC FUNCTIONS AND THEIR APPLICATIONS 5 AH [8(Hewo) + 2(Hoo))—((Hono,) +3(Heo] [3(— 149,560) +2(1,280)]— [(— 267,110) +3(1,330)) 448,680+2,560-+267,110—3,500 ~ 188,000 ealories per tole of C10. In the simpler case of the formation of a single compound from its elements, aA+bB———~eC, the difference in heat contents, AH y=c(He)—a(Ha) + (Ha), is called the heat of formation. Since the heat content of an element at 208° K. is defined as zero, the heat content of a compound at this base temperature is equal to the heat of formation from its elements at 298° K. ‘The additive property of heats of reaction has long been known as Hess’ principle. Ap- plication of this concept permits the determination of the heat of reaction by simple addition or subtraction of heats of formation at any given temperature. Examptx 3: Determine the heat of reaction for the reduetion of dichromium trioxide by caleium at 500° K. Reaction: Or0s+8 Ca- 3. Ca0-+2 Cr 1, 8. Ca4-3/20,——— +3 Ca0 Affao=3(—151,650) 454,950 calories per 8 moles CaO. 2. 2Cr+3/20;————+Cr05AHgo= ~271,850 calories per mole Cr,Os. Subtracting (2) from (1): Cn0,+3 Ce Ca0-+2 Cr AHim= —183,100 calories per mole. HEAT BALANCE Most unit processes for extracting and re- fining metals involve a transfer of heat energy to or from the surroundings. The necessit for ‘maintaining optimum temperatures, while conducting metallurgical reactions, the. re~ quirement for additional energy to sustain endothermic reactions, and the removal of heat energy to condense gaseous products illustrate a few of the processes in which heat transfer plays an important role. ‘The supply and utilization of beat rank in importance with the supply and demand of raw materials when evaluating costs and when determining the feasibility of a process. Accordingly, a system of energy accounting, or heat. balance, represents one of the indispensable tools that a metallurigist can use. ‘The law of conservation of energy is the basis for all heat balance calculations. This 3 can be stated simply for a definite system as follows: Energy input—energy output-+energy accumulation; or in terms of heat: Heat input=heat output-+-heat accumulation. ‘The heat balance must be based on an arbitrary fixed quantity, which may be a single batch of material charged into a reactor, a unit quantity of throughput, or the through ut for a fixed time interval. Since the heat content function is independent of the path of a given process, only data dealing with the initial and final states of a complex process are required. ‘These data consist, primarily of the material balance, giving juantities of substances entering and leaving the process, information on the temperatures and physical states of the input and output substances, and a knowledge of any heat transferred to or from the system. With these data, heats of reaction as well as heat, contents of all substances involved in a reaction can be evaluated. An accounting of all energy involved in a system can then be determined ily. A schematic diagram of a hypo- system will facilitate analysis of the problem. Exampie 4: In the extraction of metals by chlorination, condensers are employed to recover a volatile chloride product. An evaluation of the heat duty on a condenser, and in turn, the valuation of the cooling water requirements, illustrates the simplest form of a heat, balance. Yonsider the condensation and solidification of 1 mole of tungsten hexachloride (WCI,) as illustrated in the following diagram: wok WCl, Oh00® } Gor. HO ho @ 350° K, @ 208° K, Heat lost by WCl= Heat gained by water. Heat lost by WC, = Hon Ho = Hens Hs AH lost in cooling from 1,000° to 500” K. 10,000) calories per mole WCl, (9,000) calories per mole WC. (41,000) calories per mole WC, Because there are no tabulated values for the heat content of water at the desired temperature (350° K.) the empirical equation shown in6 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS part 2 under Water (p. 54) for Zone 1 must be used Hy— Hy = —5,876+ 18.087. Han How= ~8,376 18.03 (950)—934 calorios per Heat gained by 1 mole of water when heated from 208° to 350° K.=934 calories. Moles of water required to condense and solidify WC, (41,000) TM 43-9 moles HO. A slightly more complex problem is en- countered when a chemical reaction takes place within a process. Exanrve 5: In the first stage of the Kroll process for the reduction of titanium tetra Chloride by magnesium, temperatures of 1,100° K. are required to promote a reaction between molten magnesium and titanium tetrachloride, Determine the heat, requirements for the reactor when the chloride and magnesium are intro- duced at room temperature, 298° K., and heated to 1,100° K., the reaction temperature. Reaction: 2 Mg-+TiCl, ————+ 2 MgCh+Ti 2 Mg 2 Mg Ch G@ 208° K. ]_@ bow! x 1,100° K. | Tic @ 288° K. Ti @ 1,100° K. Q ‘This evaluation can be accomplished by following any desired path through the process, since the change in heat content is dependent on only the initial and final states. Calcula- tions are often made using either the base temperature, 298° K., or the reaction tempera~ ture as the reference temperature. ‘The following calculations illustrate each method: 1. Evaluate the heat input and output with reference to 298° K. The heat of reaction at 298° K. will be calculated as was done from the heats of formation of the compounds. In all calculations it must be remembered that the heat content of elements at 208° K. is zero. AH reaction at 298° K. BAH sac, sb 298° K.) ~alfnicy at 298° K. 2(— 158,200) —(—181,400) 125,000 calories per mole Che Since the heat of reaction is negative, the reaction is exothermic; consequently, heat of reaction is a heat input term. Heat balance: Heat input—heat output; Basis: 1 mole ‘TiCl reacting. Heat input: ‘a, Reactants: Since each reactant is at 298° K., there will be no heat input due to the reactants, b. Heat of reaction: —125,000 calories. Since the heat of reaetion is exothermic, heat will be added to the system. Total heat input= 125,000 calories. Heat output: a, Products: ‘Titanium, Hh, 10—Haes=5,030 calories; magnesium dichloride, 2(Hy 1w— Hews) =2(25,050)=51,900 calories b. Heat loss: Q. Total heat output=57,500 +Q._ Since heat input—=heat output, 125,000 =57,500+.Q and Q=67,500 calories per mole of TiCl, reacted. 2. Evaluate the heat input and output. with reference to the reaction temperature, 1,100° K. ‘The heat of reaction at 1,100° K. will be cal culated using heats of formation at 1,100° K. AH reaction at 1,100° K. (AHyct, at 1,100? K.) =AHricy, at 1,100° K, (= 141,750) — (— 180,000) 102,600 calories per’ mole. ‘The reaction is also exothermic at this elevated temperature; accordingly, the heat of reaction is a heat input. term. Heat input: a, Reactants: Although the reactants are in- troduced into the process, their heat inputs are negative values because their temperatures are below. the reference temperature of 1,100° K. ‘Titanium tetrachloride: Hsss—Hh,10=—19,965 calories; magnesium: H2—H,, 0=2(—7,700) =—15,400 calories. b. Heat of reaction: 102,600 calories. Total heat, input=102,600—35,400=67,200 calories. Heat output 8, Products: Since each product is at the reference temperature, there will be no heat taken out by the products. b. Heat loss: Q. Total heat output=Q. Since heat input—heat output, Q=67,200 ‘calories per mole of TiCl, reacted ‘The slight variation in answers is due to rounding ‘off of all heat-of-formation values in order to report them only to their known reliability. Another heat balance problem which commonly arises is the evaluation of the final temperature of the products when the reactor is assumed to be adiabatic (that is, insulated in a manner that eliminates any heat transfer in or out of the system) or when the heat input or removal is known,THERMODYNAMIC FUNCTIONS AND THEIR APPLICATIONS 7 Exampre 6: Tungsten trioxide (WO,) is reduced by hydrogen to tungsten metal when the reaction is conducted above 700°C. Determine whether the products produced in an electrically heated furnace are above the minimum 700° C. if 60,000 calories are added to the system for exch mole of WO; reduced. Reaction: WOs+3Hy>————+W+3H1,0 WOs 3H,0 @288° K, Hr 3H w @208° K. ery K. ,000 calories Since the reaction temperature is unknown, a reference temperature of 298° K. will be used. Heat of reaction at 208° K. will be calculated from heats of formation. ‘The heat, of formation for elements at their standard state is zero. Hmm =3(AHao)~AHwoy (68,320) — (— 200,850) = 204,050-4 200,860 = 4,160 calories per mole WO, Once again, the reaction is exothermic and the heat of reaction is a heat input term. Heat balance: Heat inpu of Heat input 1. Reactants: Since each reactant is at the reference temperature, 298° K., there will beno heat input due to the reactants, 2. Heat of reaction: 4,100 calories. 3. Electrical input: 60,000 calories. heat input = 64,100 calories. Heat output: Products: Each product will carry out heat at the unknown temperature, 7. "From the equation for the reaction, the fotal heat output will be equal to three times the heat content of water plus the heat content of tungsten. Tt will equal the total heat input. Total 64,100=3(Hp— Hon) Ha0-+ (Hp— How) W. The evaluation of the temperature requires a trial-and-error solution, assuming various temperatures until the correct temperature balances the above equation. TeK, | strata HyO+ctr—Ha0W | Total heat carp aaa r ee: i e388 ‘The products will leave the reactor at a temperature between 1,200° and 1,300° K. FREE ENERGY ‘The thermodynamic function which provides the means to evaluate the feasibility of a ven chemical reaction under specified con- litions is free energy. Any reaction or process thit takes place is accompanied by a change in the free energy of the system, and this change is equal to the mechanical work done by or absorbed during the process. ‘The magnitude of the change in free energy becomes a measure ‘of the tendency for the reaction to proceed under stipulated conditions. For the general chemical reaction, aA+bB——1rR +88, the change in free energy at a given temperature and pressure is given by the van’t Hoff reaction isotherm, aFe=—RTinK +R Tin where K is the equilibrium constant of the reaction and da, ds, a4, and dy are the activities of the various products and reactants at the given temperature By definition, the setivity of a pure liguid, slid, or gas is equal to unity. When all of the reactants and products are in their pure standard state, that is, all activities are unity, the change in the free energy is termed the standard free-energy change, AF; The isotherm relationship becomes -RTInK, and for the van’t Hoff reaction isotherm, ‘The direct relationship between the free- energy change and the equilibrium constant, , is valid only when all of the activities are unity; that is, all reactants and products are in their pure state, In cases involving solutions, the activity correction factor should be considered. Since there is very little information available on the activities of substances in solution at high temperatures, it is generally necessary to assume that the activities of each component in liquid or solid solutions are equal to their mole fractions, and the activities of the components in gases are equal to their partial pressure. Calculations involving free-energy changes are most frequently made to assess the feasi-8 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS bility of chemical reactions. ‘The simplest interpretation of the free-energy change is that reactions resulting in a Joss of free energy are thermodynamically possible and are likely to proceed farther toward completion as the change in free energy becomes increasingly negative in value. “It is Important to emphasize that the free-energy change accounts only for the driving energy available and cannot predict the resistances to a particular reaction or process. Therefore, it, is impossible to predict the reaction rates by the free-energy change. | ‘When the free-energy change is zero, the reactants are in equilibrium with the products and the constant, K, becomes equal to the activity factor or equal to unity, if standard state activities are assumed. A positive change in free energy indicates a tendency for the reaction to go in the reverse direction to that in which it is written. If the free-energy change is more positive then 8,000 to 10,000 calories, there is a general tendency to’ dismiss the process as thermodynamically impossible under ‘the conditions specified. Altering the conditions to operate at different temperatures, or at cither higher or lower pressures, could alter the feasibility of the process. In’ addition, sub- sidiary reactions might alter the enengy balance 80 as to bring it within the preseribed limits ‘The free-energy change during a process is related to the heat content or enthalpy change by the following equation: AF r=aHr—TASr, ‘This empirical relationship states that the energy available for mechanical work 8 equal to the total heat energy evolved or absorbed less 4 term, TASz, which accounts for energy lost due to irreversible factors such as friction. This latter term is a product of the temperature at which the process takes place and the change ih entropy, which occurs with’ the process Because this bulletin is limited in scope, no attempt, will be made to present a complete description of entropy or the second law of thermodynamics. In simple terms a change in entropy may be considered as a measure of the unavailability of energy in a system for per- forming useful work. An inerease in entropy, therefore, would correspond to an increase in the unavailable energy in a system. Quantita- tively, a change in entropy in any system is measured by the heat absorbed or evolved reversibly divided by the absolute temperature: Since the change in heat content and entropy can be expressed directly in terms of heat capacity and temperature, an empirical equation may be written for the free-energy change: are[ ote fascat fates 2G) As in the case of heat content and the heat of formation, empirical equations and tabulations have been prepared for each substance to relate the free-energy change values and temperature. The free-energy change for a given reaction can also be evaluated by simple arithmetic calculations, using values for the free energy of formation for each compound involved. ‘This determination is identical to the heat-of-reac-~ tion calculation involving heats of formation. For the general chemical equation, aA+bB—orR+88, the free-energy change due to the reaction is determined from the empirical relationship, AF y= [r(4F x) +8(4Fo)]—(a(aF a) +0(4F 9). There is no free energy of formation for the elements. ‘The free-energy function is independent of the path of a given process. Accordingly, a knowl- tdge of the initial and final states of & complex rocess or reaction permits the evaluation of the ree-energy changes resulting from the process or reaction, Probably the most important application of thermochemical calculations in extractive metallurgy involves the evaluation of the thermodynamie feasibility of a proposed reaction and the operating conditions under which the reaction should proceed. Examere 7: When preparing yttrium metal, yttrium halides are reduced with active metals. Determine whether calcium and/or magnesium can be used as reducing agents if the reaction is conducted under 1 atmosphere pressure. If the reaction is feasible, evaluate the temperature range in which the reaction can be conducted. ‘The free-energy change associated with each reaction will be calculated, using ‘the free energy of formation for each of the participating compounds. 1. Magnesium reduction: 8 Mat? VOW 8, MgChey 2Y. AP ronstion (AF ueci,) —24F rei) Products ~ Reactants= Reaction = ap2n| imo! cam Bac | 28 esrners 11,900222"] 99; 650, (108, 33| (a7, 0) +2, 400) Employing estimated free-energy values for yttrium trichloride, the magnesium reductionTHERMODYNAMIC FUNCTIONS AND THEIR APPLICATIONS 9 does not seem to be feasible. 2. Caleium reduction: 3 Ca+2 YCl————~+3 CaCh,+2Y. AF reaction (AF exci) — 2a eer) Produets—Reactants = Reaction Produets ‘The calcium reduction seems to be feasible over the entire temperature range. The optimum operating temperature must be determined by the kinetics involved. Operating temperatures greater than 1,055° pared required to prevent the solidification of calcium dichloride, which might be expected to hinder the reaction ‘When unit activities for the reactants and products can be assumed, the free-energy function is directly related to the equilibrium constant by the relationship: AFr=—RT In K. Since the equilibrium constant, K, is defined in terms of the concentrations of’ substances participating in the reaction, the fre-enen change can be used to evaluate the relationship existing between the equilibrium partial pressures of the gaseous participants. Consider the reduction of a metallic oxide: MO.o+ Roz RO» Meg The equilibrium constant, K, in terms of pressure will be K,=(Pro)*. Combining these two relations: AF r= —RT In (Pro)? ‘This relationship can be used to evaluate the pressure under which the reaction can be made to proceed. ExampLe 8: Determine the equilibrium pressure of carbon dioxide when lead oxide is reduced by carbon at 1,000° K. according to the following reaction 2PbO+C————+Pb+CO, 2 at 1,000° K.= (AF) bo)—2(4Fix0) '— 94,600) — 2(— 28,250) 88,100 calories. ‘The equilibrium constant, K, can be evaluated as follows: Fy 00 im K==(987) (1,000) K=2.14X 108 AF ne 9.18, Since carbon dioxide-is the only gaseous participant at 1,000° K., the equilibrium constant, K, will be equal to’ the equilibrium pressure of’ carbon dioxide; that is, Poo,=2.14X 10" atmospheres. It is obvious that the reaction can be conducted by operating below this pressure. Exampre 9: Evaluate the equilibrium partial pressure of carbon monoxide during the carbon reduction of dichromium trioxide at 1,400° K. according to the following reaction 20r+3C0 (AF Eo) ~ (Fb) = 56,250) — (— 185,050) 16,300 calories; 5.87 Crs0,+3C ‘AF haneuoe at 1,400° K _ AF; _—16,300 RT (1,987) (1,400) K=2.78X 10>. In ‘This equilibrium constant is directly related to the equilibrium pressure of carbon monoxide: K= (Pop)? *co=0.14 atmosphere. ‘Theée results indicate that dichromium trioxide can be reduced by carbon at 1,400° K. only when the partial pressure of carbon monoxide over the reaction is less than 0.14 atmosphere. ‘This can be accomplished by operating under vacuum or by removing ‘continuously the carbon monoxide produced in the reaction in a stream of inert gas. Since the free-energy function measures the energy available to accomplish work during a proeess, it can be used to evaluate the elec tromotive force in an electrolytic cell OF N58 Where 5 is the Faraday and N'is the number of electrical equivalents involved, NS becomes the number of coulombs that pass if the reaction proceeds to completion and & is the electromotive force. With ‘AF’y expressed in calories and & in volts, the above equation becomes AFrr=—N23,0628. Examrue 10: Evaluate the electromotive force required to decompose magnesium dichloride at 1,000° K. Reaction: MgCh +Me-+Ch Because the charge on magnesium changes from +2 to 0, AF reaction at 1,000° K.=—(AFacon) 115,150 ealories, —N (33,0828PART 2.—HEAT CONTENT, HEAT-OF-FORMATION AND FREE-ENERGY DATA In the following pages are assembled tabular data and graphs of thermodynamic values for 65 elements, and their known oxides, halides, carbides, and nitrides. All data and equations are in terms of ealorie-gram mole- K. units. The tabular values incorporate a base temperature of 298.15° K. (25° C.). To-avoid any possible confusion, the state of reference at this chosen base temperature is indicated specifically in each tabular heading. In compiling these tabulations, data published previously by Kelley (79-84), Brewer (6-9, 11, 12), Coughlin’ (24), Stull (190), and Rossini, Wagman, Evans, Levine, and Jaffe (112) were of particular importance. ALUMINUM AND ITS COMPOUNDS Element, Al (c) 77 e.u.(88) 1.79 K.(82) 570 calories per atom ,600° K.(130) 7,950 calories per atom Zone I (¢) (298°-931.7° K.) Cp=4.944-2.96 10-782) 605-+4.947+1.48X10-9T? (6054.94 Tin T— 1.48 10-°724.27.197 F—Haw=330-7.00TIn T+ 37.837 10 Zone ITT (2) (1,300°-2,500° K.) (estimated (180)) (rte oo arm | ay | m8. _ — an : z Fi - |e a B is fs = Ha Ht te) ae a | fe ge tes a fe |e) if 3 ite lig). its Sa ae lee ee & =| BS (BR AB Dialuminum Oxide, Al,O (9) AHin= (—33,500) calories per mole (8) ‘Sioe= (68.2) eu. (24) Formation: 2Al+ 1/20; ————>-Al, O (estimated (24)) Aluminum Oxide, AlO (9) AH¥s= 10,000 calories per mole (8) Baa hao ca (2) : Al+1/20, (estimated (24)) —Al0 FormationHEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA ML z ag ES ae = cs & ig te He 2 i a = ie cS i as s (3,00) | 8 Dialuminum Trioxide (Alumina), 41.0; (c) 400,290 calories per mole (68) 2.16 eu. (87) 813° K(112) 8,000 calories per mole Zone I (¢) (298°-1,800° K.) y= 27 434+3.06X 10-27 8.47% 10°T-+(82) iL 155E97 497+ 153x107 $847x 107" Formation: 2A1+-3/20 Zone I (208°-931.7° K.) 6.81—4.3x 610° 77.87 10°T* 405, 2004-6,81 72.18% 10-2 724.7.87% 107+ = 405;200— 6.81 Tin 72.18% 10° T+ 3.93, 10°F 125.587" Zone II (931.7°-1,300° K.) 2.694 1.56 X10-°7—7.87 10872 408,060-+ 2.697-+0,78> 10-72 4-7.87<10°T* = 408,660— 2:69 Tin 70.78 10-*7%+ 3.93, 10°14 102.387 ———Al,05, se | am | are 216] aoa | 25.00 cad 0 | ~3nt 300 ae 0 0 Ro So) | 38k 300 Be 0 i ae 00 i 08 00 on ge 400 | 328-300 hor ‘ao | ~31"300 an oo | 300 400 sis 0 i se 0) | (= 6) Sa 0) | {=a 18) 2.8 | (Cita ow) Zr oo ae 0} | (=n) ar 300} (36910) Aluminum Fluoride, AIF (c) AHls= (—84,000) calories per mole (11) Soe= (12) en. (11) (1,t00°) K. (6) ,000 calories per mole 1,650 K. (6) ,000 ealories per mole Zone 1 (g) (208°-2,000° K.) 91.45% 1057-1 (82) Aluminum Trifluoride, AIF, (0) = 393,00 ealores per mole (11) aasew ay hme ‘1,545° K. (6) TH 000 calotes per mole Zone I (¢) (298°-1,100° K.) C,=15.64411.28X 1097 (82) Hy Hya= 5104+ 15.687 + 5.64% 10-87? Formation: Al-++-3/2F,———l F, Zone I (298°-931.7° K.) = 178+ 7.66%10°7-+1.20% 1057? = 322,400—1.737-+3.83%10-°7— 1.201071 322,400+1.73TInT— 3.83 10-°T?—0.60 X1OT+ 45.837 Zone II (931.7°-1,100° K.) 8.79 10.62% 10-*T+1.20X 10°72 323,503.70 5B 10°72 1.20% 107+ 328,500 4.8.79 T!n T— 8.31 10-°T?—0.60 X14 34327 bupbbbhes 322858225 Aluminum Trichloride, AlCl; (c) — 166,800 ealories per mole (11) 40.5 eu. (11) -465.6° K. 6) 8,500 calories per mole }.P.=720° K. (6) ‘Bis = 15,610 calories per mole Zone I (c) (298°-465.6° K.) 18,25+-28.00% 10-7" (82) 5,195-4 18.257+ 14.00% 10-*7* Zone II ()) (465.6°-720° K.) ©, Hy Ha Zone III (9) (720°-1,800° K.) ,=19.8-2.69%10°T- (94) Hy— Hu =20,320-+ 10.87 2.69 107+ Formation: Al+-3/2Cl———-Al Cl, Zone I (298°-466° K.) 4,92++ 24.05%10-°7+.1.02% 1087 166,100- 4.0974 12.47 10-7" 1.02 xiv 166,100-+ 4.02 7m P—12.47%10-*72—0.51 X10 20:317 Zone II (466°-720° K.) 4C,=13.03—3.05%10-°T-+1.0210°T 163,000't 18.087 1.52% 10-*T?— 1.02 x1012 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS AP r= — 163,000—13.037 nT'+ 1.52X10*T'—0.51 X14 11807 Zone Ili (720°-931.7° K.) 1,633.05 1097 —1.67X 10°72 —140,500-F1.687— 1.52% 10-97? 1.65% 10°T+ = 140,500—1.637In T+ 1.52 10° 7-40.83 x10°P+9.487 8828583 SEEEEEGE! Beebe SESSESEEEE R099 BERSSSERSgeEEs,. Aluminum Tribromide, AIBr; (c) — 127,000 ealories per mole (17 Gdeweuyen hence GD 710 calories per mole 789° K (8) 16,080 calories per mole Zone I (0) (298°-370.6° K.) 18.744 18.66% 10-*7" (82) Hy Hyw= 6820+ 18.747 +9.33 107? Zone II (0) (870.6°-500° K.) Formation ‘AL4-5/2Bn———ATBr, Zone I (298°-331° K.) 11,854 15.7107 = 124 20011-8574 7.85% 10-72 =124,200+ 11:85 Tin F—7.85 x 10-°T*— 62.35 Zone II (331°-500° K.) =11.0~2.96% 10-9 7+ 0.55 1007-2 ,200-+ 1.01.48 10-272 — 0.55 10°T-1 = 130,200~ 11.0 In T+ 148X 10-97? — 0.27 X1OT S27 Aluminum Triiodide, All, (0) Alfjm= —74,400 calories per mole (21) ‘Sen= (46) @.u. (21) i64° KK. (82) 8,500 calories per mole Zone I (¢) (298°-464° K.) 16.88+ 22.66% 10-7 (82) 8,040-+ 16.887 11.83 10-°T? (464°-500° K.) Zone II () C=20.0 (82) Hy—Hyx= —5,250+29.07 Formation: Al+3/2ly Ally Zone 1 (298°-386.8° K.) AC p= —2.44-41,85% 10-7 AHr= —73,800—2:4474-0,92% 10-°T AP r= ~73,800-+ 2.44 Tin T—0.92 10-772 13.247 Zone II (386.8°-464° K.) AGp= ~1.s8-4 10.7 1007, = 68,600—16.867-+-9.85 x 10-71? = 68,600+ 16.86 Tln 79.85% 10-°T?—19.76T Zone IIL (464°-500° K.) ac, — 2.96 10-27 10, =78,000+ 10.737 1.48% 10-7? =73}000— 10°73 Tin P+ 1.48 10-9724. 65.137 Tetraaluminum Tricarbide, ALC; (c) aH, Si Zone I (c) ~ 39,900 calories per mole (9) 5.2 ex. (9) (298°-600° K.) 24,08--31,6X 10 T(82) =8,585-+24.087+15.8 10-7? Formation: 4A14+3C———-— ALC, Zone 1 (298°-600° K.) T$ORE1Or x10 TLOsOX OT 150: 8.35% 10-97 6.80% 1087-1 ~Selsor S0zTinT 8 35x10 310 xIBT 46.27 e888HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 13 Aluminum Nitride, AIN (c) AHy~~64,000 calories per mole (9) Sassen ME = 2600". () Zone I (¢) (298°-900° K.) AT+7.80X 107 7(82) 1,980-+ 547 7+-3.00 10-97? Formation: Al+1/2 N-———AlN Zone I (298°-900° K.) 338X107 Zone I (¢) (298°-903° K.) BIL LTAX 10-7 (82) 1,720+5.517-+0.87% 10-7? 13720 5.51 Tin 0.87 X10 T+ 26.987 Zone II (2) (903°-1,300° K.) eH s) ese = 4 z : Be) He i Pee ie ge) tk Be ze| ie iz ee iS a3) ee ie es) he te ae) i ay) Be ES a3) BS Diantimony Trioxide z 4 (Orthorhombic), Sb,O; (c) B 109) 168, 800, calories per mole (118) * 29.4 €.u. (83) i FF he pom 2 * 1,008" K. (2) 2 81910 calories per mole & 5 Zone I (c) (298°-929° K.) 3 Estimated equation: 8 -200) CoH ITAXIOAT (2) : Ly Hy— Hoge BABE IOATEBSBXIO TD? “ 1 ie g 300 we, A] < Formation: 2Sb+3/20,——-—Sb,05, © (estimated (24)) 3 sso} “es | “400° 300 500 1900 TOO epoo HK - TEMPERATURE, *K oe " = 3 Frovne 1.—Aluminum, 2 33 i 3 ANTIMONY AND ITS COMPOUNDS isi: 0} 2 200) Element, Sb (c) ie i} 1. 00) i Hy 647040 0—e2—2 |:14 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Diantimony Trioxide (Cubic, Orthorhombic), Sb,O; (0) 169,900 calories per mole (111) atte 7 eu. (24) mu a T. 12° K. (24) 30 calories per mole MP. 028" K. (24) SH y= 13,500 calories per mole B.P.= 1,698" K. (24) 010 calories per mole Zone 1 (298°-842° K.) Estimated equation: 19.1417.1X109T (82) —6,450+ 19.17 +8.55X 10-7? (82) Formation: 38b-+3/20,———Sb.0, (estimated (24) 1k Hee | alte anh iseE55 e888 sgESEES Be 8 ¢ f £ i : i i Be EE 2B gs Antimony Trifluoride, SbF; (¢) AHine= — 216,600 calories per mole (11) ‘Sne= (88) eu. (11) M.P.= 565° K. (6) BLP.= 649° K. (8) Aify= (14,000) calories per mole Formation : Sb-+3/2Fy SbF; (estimated (11)) He-tim | anh are | CHR) (CREB 63] CEN) (its 3) Antimony Trichloride, SbCl; (c) AlTjq= —91,400 calories per mole (11) Sye=44.7 eu, (11) M,P=346.4° K. (@) ‘AH y=3,080 calories per mote BPE KO) ‘Aiy= 10,362 calories per mole Zone I (¢) (298°-346° K.) Cp=10.8-+ 51.1107 (82) Hy Hya= ~5,800 10.37 + 25.55 X10-*T* Formation: Sb+3/2Cl,h———-SbCl, (estimated(11)) Zone I (298°-346° K.) 844+ 49.26% 10°74 1.02% 10° 90,700 8.447++-24.63X10-9T>— 1.02 xO anti : 44 Tin 24.08% 10-*T—0.51 Diantimony Tetraoxide, Sb.O, (c) aR a tiat— 2 Fin (700,000) calories per mole (24) eal 1 a08 IK. (24) °K, Hr-tim | Atte arr 2Sb+20,—————Sb.0, - ~91, 400 7,0, imated (24) es Wiis] Crmano)] 7 00) Be au ou Antimony Tribromide, SbBr; (c) ~ 200, oan AH i= (— 59,900) calories per mole (11) 3 ‘Sig= 93.3 ee (11) ‘a i) MP =370° K @) f 3 ‘Sil =3,510 calories per mole 206, $00) B.P.= 561° K, (6) Q i) (12,000) ealories per mole § 3150) Diantimony Pentaoxide, Sb:O, (c) SHys= (— 229,000) calories per mole (24) Sre= 31.3 €.. (24) Decomposes = 673° K. (24) Formation: 28b+5/20,— ——Sb,05 (estimated (24)) nk Hea He ms apa] CBB | Sika) (Cr tion: Sb+3/2Br-—————>SbBra (estimated (11)) 7 F | enim | ant are ce sas! 9B) co ees] 08 00) Antimony Triiodide, Sbl; (c) — 22,800) calories per mole (11) ‘Sip= (57) ex. (11) MPa 44K. (6) P= 700° K. (6), (15,000) ealories per moleHEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 15 Formation: Sb+3/21,—————Sbl, (estimated (1) Hr-Hm | amp an Diarsenic Trioxide (Orthorhombic), As,O; (¢) Fe =157 000 ealores per mole (1 Bec abien ute vere (=, 100), T.P.= 506° K. (24) Bam Aity=4,110 calories per mole M,P.=542° K. (24) Aily=7,090 calories per mole B.P.=730.3° K. (24) ‘Hy =14,800 eslories per mole of ANOs 2 2 Formation: 2As+3/20,————>As,0 Bp ep (estimated (24)) i aq oon $ y Hiri art il : = z § 124 in & ee 3 oe cu Boy eo) ae ae = 8 ne we © -l29} 0. 8 30 5 :500--- - (40,800) -T7, 050) 3 a] ee Eee f ee ia i a1 i 2) ees zy gfe” |e 350 oh tee # sco} 5 sed Diarsenic Trioxide (Monoclinic), 8U/ [Mrs AsO; (c) 300 10 1 eH AHin= — 152,900 calories per mole (114) TEMPERATURE, *. Fieure 2.—Antimony, ARSENIC AND ITS COMPOUNDS Element, As (c) (33) Zone I (¢) (298°-883° K.) Cy=5.284-2.22%10-97 (82) Her Hog = — 1,658.4 5.237 + 111% 10-°T? = Hoyp= — 1,658~5.237In 1.11% 10-724 27.287 ‘Above 889°, diato gas (estimated (124)) | actin | Se | -@e=ttw ‘SH y=4,000 calories per mole B.P.=730,3° K. (24) ‘SHy=14,300 calories per mole of As\Ox Formation: 2As-+3/20;———>-As,0 (estimated (24)) Hr—Hos : é yy 9} a SESS88 | 88888: BSE! ESSgeSESESESESE8E3 Se sSSE5E! e a EEE aR: a g2222552822 BRaEREESS SS88858283) EESESE8: a Diarsenic Tetraoxide, As,O, (c) alt —175,500 calories per mole (14) = (88) eu. (24) Formation: 2As-+-20,———~>As,Ox (estimated (24))16 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Formation: As+3/2Bry-————AsBry Sn eee (estimated (11)) Ft soem Ar-H aH | Are a oc : ‘its i | eel oo Arsenic Triiodide, Asl; (c) Sooo Diarsenic Pentaoxide, As,O; (¢) es per mole BP.=687° K. (6) AHHi= ~ 218,500 ealories per mole (112) 4,200 ealories per mole Sim= 25.2 e.u. (112) Formation; As+3/21,———>Asl;, Formation: 2As+5/20,— —>As,05 (estimated (11)) (estimated (24)) a i —- a Hr-H ‘aH Ae [a n-nm | ane | art _ a cas! cia) igo on mgs] BS 2 ies) ARGH] Com 418 om a} a | -219, 000) 000) | Ha Clea : : sad — : a Bg | 8, eos Be Bh 25) 7 ee ‘a0 28 500) gs Of 7 ea bas} = -20 aE nd 5 ee Arsenic Trifluoride, AsF, (1) 8 ‘AHju= ~218,300 ealories per mole (112) 5 ‘Son = 69.08 e.u, (112), I AF ig= ~214,700 calories per mole & MBS pane. U2) a ‘AHy=2,486 ealories per mole = Bu 333° K. (94) w ‘SHy= 7,100 calories per mole # Arsenic Trichloride, AsCl, (I) ¥ ‘AHig= —80,200 ealories per mole (112) Sass? 8 eu. (112) AF f= — 70,400 calories per mole 20% ‘300 500 0 1500 eA M.P. 7° K. (112) ‘TEMPERATURE, °K. ue Si;= 1,500 ealoriee per mole Prove 8 Arsenic BARIUM AND ITS COMPOUNDS Arsenic Tribromide, AsBr; (c) Element, Ba (c) 46,610 calories per mole (112) le) 16.0 eu. (8) ia Ke" 112) 988° ik. (63) 810 calories per mole 1,880 ealories per atom fa" KK (112) 1911" K. (130) 85,700 calories per atomHEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA W7 Zone I (c) (298°-983° K.) 5.5541.50X10-T (82) 1,720:+ 5,557 +0.75 10-97" 1,730—5,55TIn P= 0.75 X10-*7+ 21.567 Zone II (0) (983°-1,125° K.) ‘Above 1,125° K. (estimated (130)) nee | maim | me | Pen = | i) OB m0: Ls ma 1125 HB) gt) BB ig) oH) EB z igo al) iB "i ie) aL) ORR Pa iB] G8) ae Ea & 2 G8 Be as, 28) Be @ a ee eS ie) BR) Be e fig] BE) ae i a au a ie] BS) BB Barium Oxide, BaO (c) Allju= —133,400 calories per mole (60) ‘Sie= 16.8 eu, (83) M.P=2,106° K. (8) ‘Aiy= 18,800 calories per mole B.P.=3,600° K. (8) Zone I (¢) (298°-1,300° K.) 12.74++ 1.040 10-*7— 1.984 107-2 (82) =4,500-+ 12.747 +-0.52X10-97"+ 1.084 x10 Formation: Ba+1/20, BaO Zone I (298°-983° K.) 3.63—0.98X 10-47 — 1.78 10°74 = 135,000-F3.63 70.48% 10-724 1.78 1057-1 = 135,000~3.63 Tin T+0.48 10-*77+-0.89 X14 48.777 Zone II (983°-1,125° K.) = 2,324.0.54X 10-97 —1.78X 1067+ 152,700 2.8274-0.27%10-*T*+ 1.78 107 = 152,700+2.32 In 70.27 x 10-7774 0.89 XIOT +487 ox, Hr-ttm | sr | ant | are SEuSERH BREBNEEES SERDEEBUREE! ESSuEESEUEEuREEE Barium Dioxide, BaO, (c) AHj= — 151,890 +250 calories per mole (189) ‘Siov=22.62 &.u, (24) Formation: Ba-+-O;————>Ba0, (estimated (24)) Hin | ane | are spESEzESES ee B Barium Difluoride, BaF, (c) AHi= = 286,900 calories per mole (112) 83) 08 593° K. (112) 000 calories per mole 473° K. a 000 eaiories per mole Zone I (¢) (208°-1,300° K.) Cy=13.98-+ 10.20% 10-7 (82) 600°" 13.9874-8.10% 10-97 Ba+F,———BaF; Zone I (208°-983° K.) AC p= 0.144 8.26% 10-8 7+0,80% 10°72 287,000-+0,147-+4.13 x 10-7 — 0.80% 10°T* 187, 000—0.14 Tin T— 4,13 10-°T?—0.40 x10 44487 Zone I (983°-1,125° K.) 81+ 9.76 10-37 +0.80 x 1087 284,800— 5.81 7+ 4.88% 10° T— 0.80% 10°T-* 284,800++ 5.81 7InT—488X 1097?—0.40 xO +1917 or aH are ae| eel as a3|-e2| ae #4) 228 28 #2) 88) BS Pe de (Cas ito)| aa, 200) 205,300 calories per mole (11) (29) eu, (11) 233° K. (6) '370 ealories per mole ‘100° (6) (50,000) calories per mole18 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Zone I (0) (2989-1, 198° K.) Cy=17.043.84X 107 (82) Hy— Hya= — 5,200 17. 07 $1.87 X10? Formation: Ba+Cl-————>BaC Zone I (208°-983° K.) AC y=2.08-4 1.78% 10-°T 4.0.68 1007-2 AFL7= — 206, 000+2.637'+ 0.88% 10-°7?— 0.68% 10°71 ‘AF p= — 206,000 2.63 7%nT— 0.80% 10-97? 0.34 X08" 58.137 Zone IT (983°-1,125° K.) AC p= —3.824+3.28% 107+. 0.68% 1074 = 303,400 3327+ 1.64% 10-*7*— 0.68% 10°7- = 208/400 3:32 Tin T= 1.64% 10-97 0.34 x1 +4687 | § Tribarium Dinitride, Ba,N; (c) tf 590,600 ealories por mole (9 Desamposes=,270° K. () Formation: 3Ba-+-N,————>Ba, (estimated (9)) ox, ar | nox | Hirtim| sr | ant = asl gee) —me | «0 s er . . B Be po = ei ; < ie Fs =e 3 20." co F Bt to 3 od aca Z -2 ben Barium Dibromide, BaBr; (c) & so} ose BaBr, & 220) he (estimated (11) 2 aoe ac 240} = ca -260 a 300 OOo 00 ‘2000 (6,800) ealories per mole (2,000") K, (6) (45,000) calories per mole Formation: Ba+Iy —Bals (estimated (11)) urotw| sr | ane | art am | ag | «143. op am) isk Ciao | Ba) CH | S20) 20) 18 0) ‘TEMPERATURE, "K Frovre 4—Barium, BERYLLIUM AND ITS COMPOUNDS Element, Be (c) 28 eu. (83) 550° K. (112) 300 ealories per atom 243° K. (138) 3,490 calories per atom Zone I (c) (298°-1,300° K.) 40+2.90% 10-7 (82) 143+3.40741.45% 10-17% 1438.40 Tin T— 1.45 10-*T9+21.347HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 19 Heth & lo ial i) it i) oH Hl is it] 38 i] i ig] is ae dh a3) | | | Beryllium Oxide, BeO (c) ‘AHju= —143,100 calories per mole (22) ‘Sin=8.87 eu. (83) MP=2,803" K. (42) ‘Hy = 17,009 ealories per mole B.P=4,533° K. (42) 17,000 calories per mole Zone I (c) (298°-1,200° K.) 4544.00 10-97—3.17 x 10°T-+ (82) S Sao Sor + 2.00% 10-74 3.17 Zone II (c) (1,200%-2,000° K.) (estimated (24)) 1,47 40.60% 10-°7—2.97 x 10°7-+ '44,800-+ 1.47 74-080 10-9T?+2.97 1087-1 144,560~ 1.47 Tin T— 0.30% 10-9724 1.8 X1OT 435.157 1°. Het iS GERUEEEES S| aetauasess BS 2 HH Formation: Be+F,———>BeF, (estimated (11)) Beryllium Dichloride, BeCl, (¢) = 112,600 ealories per mole (11) 23) eu. (11) 78° i. (6) 3,000) calories per mole (820°) K. (6) (25,000) calories per mole Formation: Be+Cl,-———>BeCl, (estimated (11)) x atm) os | ane | are Beryllium Dibromide, BeBr: (¢) 79,400 ealories per mole (17) 29) eu. (11) 761° K. (3) 4,500) calories per mole '800°) K. (6) (22,000) calories per mole, Formation: Be+Bry —BeBr, (estimated (17)) Beryllium Diiodide, Bel. (¢) (89,400) ealories per mole (11) (31) ew. (11) 758° K. (@) (4,500) calories per mole 700" K. (6) ‘AHy= (19,000) calories per mole Formation: Be+I,———~Bel (estimated (11))20 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Triberyllium Dinitride, Be,N: (c) BISMUTH AND ITS COMPOUNDS AH= —138,500 calories per mote (61) . ‘Senden (6) Element, Bi (c) MP2 iO ke O Zone I (c) (298°-800° K.) 3.8 eu, (85) MP =548.5° K. (62) ,600 ealories per atom 832° K. (130) ‘AHy=36,200 calories per atom Zone (c) (298°-544.5° K.) 4.49+5.40% 1097 (82) ~1,579+ 4497+2.70% 10-97? = 1579 4:49 TI T—270% 10 T+ 18.087 7.82430.8X10"7 (82) c, Hy~ Hau 38,3504 7 327+ 15.4 10-97? Formation: 3Be+-N;———>Be,N; Zone I (298°-800° K.) Tt e00 0 S1 10.543410-"72 Zone II (0) (544.5°-1,800° K.) 181.600-+9:54 Tin T— 10.54% 10-*72— 18.147 es 3 i Be] Be Be |) g ye) EW) eg = i) aa) = iB ae) Re & 8) BR) Bi ee) BE) ORS i iB) BE) i HB) GE) BE iB iB) Bel 8s or 1 10,60, ae 285 u ne) Bip Bar iB ue) 82) Be 2 iz be) ga) Be : ie ae gs) gs e a 000. (68, 970)| (54.18) (28:15) Fach on 3-60} Bismuth Oxide, BiO (c) 3 ‘AHinw = — 49,850 calories per mole (112) 2 80) Sia (16.4) eu. (24) & -109 Formation: Bi-+1/20,———BiO o (estimated (24)) 8 rad Bat ow LF an B aug r a] aR 2 S| che E x69 8) ee A 2) CEB “ey a) te 20 Pea 3) ee 300 800 10001800200 smh] (=i Bo rear" ge) Es 3) Ficure 5.—Beryllium,HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 21 Dibismuth Trioxide, Bi,O; (c) as 16.2 eu, (83) MP'=1,090° K. (112) ‘AiTy=6,800 calories per mole BP.=(3,160°) K. (94) 187,000 ealories per mole (112) Zone I (c) (298°-800° K.) ¢ Hy Hs Formation: 2Bi+3/20,— 4.74+8.00% 10-7 (82) = 7,732-4 24747 $4.00 10-87? —Bi,0, Zone 1 (298°-800° K.) AC,=5.02—4.30% 10-*T+.0.00% 1087-2 189,000-45.02 72.15 10-°72— 0.60% 107+ <= 139,000—5.027In T+-2.15 10-9T=—0.30 X1OT406.57 Above 800° K. (estimated (24)) SBEREE SRBBERES: Seeeeecsea! (= 216,000) calories per mole (11) oe = (34) e.u, (11) M.P'= 1,000" K. (@) ‘afl (0;200) calories per mole 300°) K. (6) {88,000} enloses per mole Formation: Bi+3/2F.— (estimated (11)) —BiF; Hie-tim | ante | art |) cae can 90,500 ealories per mole (11) Spaa58 ou. UD) 2,80 clones per mole we 17,854 caoties per mole Formation: Bi+3/2Cl;-———>BiC, (estimated (17)) = 60,000) calories per mole (11 Sew » 191° K. (6) (4,000) calories per mole B.P.=734° K. (6) ‘SHy=18,024 calories per mole Formation: Bi+3/2Br;————BiBr, (estimated (17) Bismuth Triiodide, Bil, (¢) AHig== 23,700 calories per mole (11) Sip= (59) en (11) MER Decompones Formation: Bi-+-3/21,———_Bi. (estimated (11) 73° K. (6) Ps ; 8 03 & AF, FREE ENERGY OF FORMATION, keot/9, —mole 8 ar .-7 | 300 5000001500200 TEMPERATURE, *. Fioure 6—Bismuth.22 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS BORON AND ITS COMPOUNDS Element, B (c) Aen. (7 $00". Cen '300 calories per atom Zone I (¢) (298°-1,200° K.) Cp= 1.544440 10-7 (82) 655 +1.547+2.20% 10-27? =055— 154 Tin 2.20 10-97? 10.217 nex. | aetm| se | ane | aFE er 3) 28 Se) 28 | eS 238 | Se ae se ae 28) BB 28) 28 Be] Be Ee CEB CB es BE roe | Heim | [et 7 = ule a Hl if 0 ; be 20 ES ij] oH ee fee s ig) oH = ig) Oe = ea] Gk = a) eB : c=] ans Boron Oxide, BO (9) ‘AHin=5,300 calories per mole (112) ‘Son =48.60 e-u. (83) 11,600 calories per mole Diboron Trioxide, B.O; (c) aH: = 305,400 ealories per mole (112) 13,04 2.u. (83) 5,500,ealories per mole 2°30" K. (42) ‘aly = (70,000) calories per mole Zone I (¢) (298°-723° K.) 8.73+25.40% 10-97 — 1.31 1087-4 (82) 4170-8737 + 12.70 10° T+ 13 x1Or Zone IT (I) (723°-1,800° K.) 30,50 (82) 7,500+80.50T Formation: 2B+3/20,———- Zone I (298°-723° K.) 5.09-415.1X10-°T—0.71 x 1087 = 304,690—5.097-+7.55%10-* 7240.71 x 107+ = 304,690 5.09 Tin F—7.55% 10°77 +-0.355 X1OT 434.37 Zone II (723°-1,200° K.) 16,687— 10.3 10-*7$-0.60%1097-* = 308, 150-+16.087—5.15 x 10-*T?—0.60 x10 308, 150—16.68T%n T+5.15X 10-*T*—0.30 X10 178.257 >B,0s Boron Trifluoride, BF; (9) 278,500 ealories per mole (42) 70 eu. (112) 145° K. (6) 190 calories per mole =172.2° K. (6) 620 calories per mole Zone I (g) (298°-1,000° K.) 2.444 6,70% 10-T—2.12 108T- (82) 4,704 12447 +3.85X 1077 4+2.12 x10 Formation: B+3/2F;————BF, Zone 1 (298°-1,000° K.) = 1,544 1.64% 10-97 0.92 1067+ 273,420 1.547-+0.82%10-*T2+.0.92% 1007-1 73,4204 1.54TIn T—0.82 X10 T+ 0.46 KAO 4.547 zasueage jBaaeease Segeegeeegeeseseee Boron Trichloride, BCl, (9) AHn= —94,500 ealories per mole (112) ‘Sipe 69.29 eu, (112) M.P= 166° K. (6) 500) calories per mole 85.6° K. (6) 5,700 calories per moleHEAT CONTENT, HEAT-OF-FORMATION, Zone I (g) (298°-1,000° K.) 16.86-+2.86% 10-°T— 2.441057 (82) 70+ 6.867 +143 X 10-9774 2.44 x1 Hr—Hia= Formation: B+3/2Cl;————>BCl, Zone I (298°-1,000° K.) 2,001.68 X10-97— 1.42 10°72 —95,525+2.097— 0.815 10-9724 1.42 x10 AF r= —05,525—2.09TInT+0.815X 10-7? 40.71 10°14 26.687 ox | mem) ose | ane | are e 28 ei ct te Bg SRREBEER sennenas BSeueeee recs: Et oe ak om oh: ne Ee ot at EEE <1 Gi q Boron Tribromide, BBr; (I) ‘Hin = = 57,000 calories per mote (120) ‘ily= (700) calories per mote Bea waa KO) 298 calories per mole Zone I (g) (364.4°-1,000° K.) Cy=17.88+2.04X 10-9 T— 1.95% 1097 (82) Hy— Hon 7,160-4 17.837 +1,02X 10-9724 1.95 x10 Formation: B+3/2Br;———>BBry Zone I (400°-1,000° K.) ACp=2.73~ 2.36% 10-°T— 1.40% 1087-4 AH p= —57,400-+2.737— 1.18107 72+ 1.40 x1oT AF p= —57,460—2,73 Tin T+ 1,18X 10-97? +.0.70 X14 32.817 = | 3 ie Re 3 Tw. ma 300 = | 23) 2 BS | a) 3 be | fe 3 BB =| a 3} iB sa 3 Bs ea 2 ES 285) o 23, Boron Triiodide BI; (¢) 27,600) calories per mole (11) (55) e.u. (11) ae po enlories per mole 16° K. 1,000) ‘calories per mole 183° K. (6) ‘AHy= (10,000) calories per mole Tetraboron Carbide, B,C (c) —13,800 calories per mole (122) ‘Sp 6.47 eu. (83) MP.=2,623° K. (9) Zone I (¢) (298°-1,200° K.) 22.99-+ 5.40% 10-37-1072 1017-2 (88) 10,690-+22.997+ 2.70% 1 x1OT Formation: 4B-+-C———~B,C Zone I (298°-1,200° K.) 2.73—18,22% 10-9 78.02% 1087-2 '20,000-+ 12.73 76.61 10977 +8.62 x0 20,000—12.737InT+6.61X10-*7+4.31 X1OT$ 87.77 5 F 2 & 5 3 eeuoeey BERESEEEE! BUEERS pow. Seeenupeccee geseanissces BBEEE Boron Nitride, BN (c) 60,700 calories per mole (33) 67 eu, (83) 270° K. (9) Zone I (¢) (298°-1,200° K.) 8447.24 10-7 (78) 380+ 3.647 $3.02 X 10-47 Formation: B +1/2N-———BN Zone I (298°-1,200° K.) aGy= ~12842.88% 10-7 BBT+1.16 1097 00'980+ 1287tm 1 LOK 10-4004 324 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS om | arm | sr | ane | art : | mearim | sr | _ Chretien | | fit) =SRO) =eRSO as. Be, Pv yie| 8h) eke | eGo Mec: cur] 4 | id a7 | asm ce] a 8 Be sip | asm ne | 8B Re ifn Tints | Ii RM im | fa a8 30 Rao) =) Sh Hon | at BB se in| I fe Bim | Bie ae oes ree) etm ior | Rat Bo aie 38) Ee | ke| 38 fe 1 aa es ae ae i ft] ee a i ie) Be ae i ae ae ao) te t : 20) t | eis] Sa a | 3 Bt "60 8 $ eo CADMIUM AND ITS COMPOUNDS 2 1 j Element, Cd (0) 8 red = 2.37 eu. (28) z +40 MPSS) a7 y lories per atom 5 038° K. (7) = +104 ‘aly =23,870 calories per atom g ee 27 Zone I (c) (298°-594° K.) ty 220) Oy=5.81 2.94 10-97 (82) # Hy— Ho LTA 53 THAT X OT? be 240) Pr—Hye= —1,714—5.31 Tin T— 1.47 X 10° T+ 24.077 cool ME Zone II ()) (594°-1,038° K.) soo Hy—Ha= CSS 0 . 300 800 POO. BOO 2000 fr How — 810+ 7. ‘TEMPERATURE, *K Pr— Hyg —810—7.10TIn T+ 32.997 Froure 7.—Boron. Zone III (g) (1,038°-2,000° K.) BROMINE 6.0) (141) Element, Br; (1) '940-+9.087-+0.37 x 1097-1 /940— 9.04 Tin P+-0.185X 10°T-140.517 mim | eet Sie=36.4 e.u. (83) T VEER on — 1) ete Pr aa 2 al 3 ree B @) #) Bisa Ble atl per atom = B) | = | | = if| 32] ti is) 38) 8 i 2B) ao) a8 i cal] 3 be va) fen 2» ie am) es) 28 Zone II (g) (331°-1,600° K.) ke. 700) is 72) 0) reatieeea He aS} 88] 88HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA Cadmium Oxide, CdO (c) AHia=—61,200 calories per mole (98) ‘Siw= 18.1 0.1. (24) Formation: Cd+1/20- (estimated (24)) =Cd0 1k, SSS8858 Cadmium Difluoride, CdF, (c) ‘AHiw= — 167,000 calories per mole (11) ‘Sme= (22) eu, (11) M_P.=1,383° K. (6) ‘iy =5,400 calories per mole BP.=2023° K. (8) ‘AHy=52,000 calories per mole Formation: Cd+F,———>CdF; (estimated (11)) Cadmium Dichloride, CdCl, (¢) ‘AHie= ~93,000 calories per mole (112) ‘Sqs=31.2 eu. (83) MP.=841° K. (6) fy =5,300 calories per mole BP.=1240° K. (6) ‘ify =28,860 calories per mole Zone I (298°-800° K.) Com Msesocoxigsn (3H Hyr— Hya=—4,700+ 14.647 +4,80% 10-97? Formation: Cd-+Cly Zone I (2989-594 K.) 0.514.6,60% 10-7 0.68 1057-2 = 93,215+0.517+3.30 10-¥7>— 0.68x 1087-1 = 95,215— 0.51 7inT—3.30X 10°79 0.34 X1OTA4 39.487" Zone II (594°-800° K.) ACp=— 1.28+-9.54X10974.0.68X 10°74 = 94,100—1.287+ 4.77 x 10-279 0.68% 1071 5941004 1.287 T— 47x 10-9 70.34 x1 +3057 —CdCl, & an ‘BgSEE882 Cadmium Dibromide, CdBr; (¢) Hig = — 75,800 calories per mole (11) ‘Sye=34.4 2. (99) MBB’ Ke ( ‘Ally 5,000 calories per mole BP m1 136° K. () ‘4Hy=27,000 calories per mole Formation: Cd+Bry———>CdBr, (estimated (11) -r20} AF FREE ENERGY OF FORMATION, kcal./g. -mole 140} 300 500 1200500, TEMPERATURE, *K. 2800 Frovae 8 —Cadmium.26 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Cadmium Diiodide, Cdl, (c) = 48,750 calories per mole (11) 39.5 eu. (11) 860° K. (@) 3,060 calories per mole 1009" K. (6) 25,400 calories per mole Formation: Cd-+I,———Cal, (estimated (11)) Zone I (ec) (298°-1,800° K.) 1.674 1,08X 10-7 1.56 X 107-4 (82) 4050-1 11.877 +-0.54% 1097+ 1.56 xan Formation: Ca+1/20,——>Ca0 c, Hy—Hya= Zone I (298°—673° K.) 2.85—2.92X 10-°7—1.38x 10°72 152,950-F2.857—1.46% 1072+ 1.36 1087-1 152,050—2.857InT+1.46X 1097+ 0.68 X1OT 443.877 Zone II (673°-1,124° K.) 80 082x 10-4 138x102 CALCIUM AND ITS COMPOUNDS Element, Ca (c) 15 ealories per atom 124° K. (80) ‘iy =2,230 ealories per atom BP.= 1,760" K. (130) 40 calories per atom Zone I (a) (298°-673° K.) Cy=5.24+3.50X 10-97 (82) Hyg TBE SAT LTO 104TH Pr Fn Zone IT (8) (673°-1,124° K,) y= 6.204 1.40% 10-7 (82) Hy— Hyg 1 834-+0-297-+-0,10% 10-472 Fp Hoa= — 1834 6.20 Tin F010 10724 32.497 = vs) as ss @) ae) Be & eB) HR) Re & He) HE) HR B He) Re) Be & SB) Ge) Be ae ee S| Be) ae S| 2s) Ee | aes] BSS] aR Calcium Oxide, CaO (c) 151,790 ealories per mote (67) 8 a (88) 873° K. (112) 2,000 exlories per mole 800° K. (94) = L718 5.247 T—1.75X 10-44 26,13T nee BEBE ‘BESgEEaEERE BRED 156,500) calories per mole (24) = (15.8) eu. (24) ‘Decomposes 548° K. (8) (estimated (24)) 338 Calcium Difluoride, CaF; (c) ‘AHin= —290,200 ealories per mole (112) ‘Sye= 16.48 ou. (134) "Pr 1,424° KK. (82) 140 calories per mole 091° K. (82) ‘AiZy=6,780 calories per mole 145° K. (112) 8,000 calories per mole Zone I (a) (208°-1,424° K.) 14,30-47.28x 10-8 7-40.47 X 1057 (88) = 4400-414 307+3.6410-97!—0.47 x10HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 27 Zone II (8) (1,424°-1,691° K.) Cp=25.8142.50% 1047 (82) Hy— Hum —14,900+ 25.8174 1.25% 10-97* Zone IIT (0) (1,691°-1,800° K.) 23.90 8 Pea 007 Ce Hr~ Hy Formation: Ca + F, ————> CaF, Zone I (298°-673° K.) T743.34X 10° T+ 1.27 X10°T-* 290,150-40.77 7+ 1.07X 109 T—1.27x 1071 = 200,150— 0.77 Tin T— 1.87 x 10-7? 0.63 IOP 47.487 Zone II (673°-1,124° K.) = 0,.28+5.44 10-974 1.271007 = 200,010—0.287+2.72% 109 T= 1.27 1087 = 200,0104-0.28TIn 72.72 1097? 0.63 xo +a Sr aH; “ate es Poe es BEBE, 190,400 calories per mole (94) Deu G8) 780 calories per mole 300°) K. o 15,000) calories per mole Zone I (c) (298%-1,055° K.) 1718+ 3.04% 10-4 T— 0.60 10°T* (83) A5,4004 17 18T-+1.52%10-"724-0.00 xiort Zone II (2) (1,055%-1,700° K.) 70 (83), Ce: Hera How Zone I (298°-673° K.) AC, =3.12—0.52X 10-°T+-0.08X 1057-4 191,280-+3.127 0.26 10> T!—0.08, x1er 191,280—3.12 Tim T4-0.26% 10-* 70.04 X10 456-417 Zone II (673°-1,055° K.) 07-+1.58X10-*T40.08 10°7-* 91 150-+2.07 7 +0.70%10-"T2—0.08x 1087-1 191,150 2.07 7%n 0.79% 10-°7"—0.05 X10 50.827) Zone III (1,055°-1,124° K.) 59— 1.46% 10-* 70.68 1057-2 1.597 0.73 X 10-¥T?+-0.68, 190,500—9.59 Tin P+0.78 10-°T?+0.34 X10°F"1+ 100.697 | | enesr BRSENEE, EesseseEsess: SERBRESERERES seresee-geacé = 161,800 calories per mole (144) 31) eu, (114) 088° I. 6) 180 calories per mole 2.100%) K. () 50,000) esiories per mole Formation: Ca+Bry——>CaBr, (estimated (11)) | tet ‘g0) 3 90} {at 10) Calcium Diiodide, Cal; (c) — 127,500 ealories per mole (112) (34) elu. (112) (013° K. (6) 3,000) calories per mole 1,500") IK. (6) (35,000) ealories per mole Formation: Ca+I,———>Cal, (estimated (11)) | aemttm | ante | ar28 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Calcium Dicarbide, CaC, (¢) AH n= — 15,000 ealories per mole (112) Sie= 16.8 6.u. (83) TP = 720° K (82) AH;=1,330 calories per mole MP.=2573° K. (9) Zone I (a) (298°-720° K.) C= 16.404.2.84X 10-4T—2.07 x 1087-4 (82) Hy— Hy = ~5,100+ 16.407 +142 10-972 +2.07 x10 Zone II (8) (720°-1,300° K.) Cy=18.40+2,00X 10-97 (82) Hy—Hy=—3,150+ 15407 + 1.001097? Formation: Ca-+20C————>CaQ, Zone I (208°-673° K.) AC p=2.96—2.7X 1047 +2.13X 10872 AH}= 1500+ 2.987 —1,38% 10-472 2.13 107-1 ‘AF p= — 15,000—2.967In F.1.35% 10-97 LLG IOT 13797 Zone II (673°-720° K.) AGem Lt asoxcto-a 43x ions attr “14 700+ L817 O40xI0 aT 2 sapcoer™ =14'700— 1.917In T+-0.30X 1071.06 X1OT4 7.027 Zone III (720°-1,124° K.) 0.91 1.44% 10-7 -+4.20% 1087-4 12,320+-0.01 T— 0.72 10-*T?— 4.20 1067-1 0.91 Tin T+ 0.72 10973 2.10 3177 RERSREREES sagccescee Tricalcium Dinitride, Ca; N2 (c) 106,200 calories per mele (9) 468° K. (112) Zone I (c) (298°-800° K.) Cy=20,444.22.00% 10-47 (82) Hy—Hon= —7,100-+20.44 7+ 11.00% 10-97? Formation: 3Ca-+N,— >CasNy Zone I (298°-673° K.) 1,944.10.48% 10-*7 108,100— 1.947 +5,.24x 10-7? = 108,100 1:94 Tin T— 5.24% 10-47 + 40.467 Zone II (673°-800° K.) BC p= —5,09-+16.78% 10-97" AHz=—107,670—5.087+8.39% 10-47 ‘AF r= — 107,670-+5.09TInT—8.39X 10-*72+21,287 He-tin| sr | amp | arp age | ing 200 | 08,0 | Tinto) Seino fa) Zien | “sa ee) Tins) Tia S| Liorton | = 590 Se80 | “ieee00 | 68,700 cxce z . ay . CO, Zone I (298°-2,000° K.) =0.71-40.14% 10° 740.48 10°T-* = 95,650—0.717+-0,07x 10-*72— 0.46 10°T-1 = 93,650-+0.71 Tin 0.07 x 10-7? 0.23 X10 5.587 47040 0833 Foe [tent | Pr an a) Bt xB| ee ig) 83 i) Be i] 28 ig| BB iB) ge iB) BR ae) Be ae) 58 tg| 88 am) aR cel ie BB) 38 2B) 8 Carbon Tetrafluoride, CF; (9) = 162,500 oalories per mole (106) ‘Sim = 628 eu. (80) M.P.=80.47° K, (106) 4Aily=167 calories per mole B.P=145.14° K. (108) ‘4H; =3,010 calories per mole Zone I (9) (298°-1,200° K.) y= 16.64-47,84% 10-97 4.001057 (79) Hy Hau ~6,850-+ 16.647 +3.92X10-°7?-44.00 X10 Formation: C-+2F,———> CF. Zone I (298°-1,200° K.) 4.044. 5.94% 10-97—0,30x 1087-4 181,700—4.047-+-2.07 10-97" 4.0.0 1057-1 161,700-+ 4.047¢n 2.97 10-72 40.15 x107+1087 Carbon Tetrachloride, CCl, (I) ‘Hin = 98,200 salaries per mole (112) 283 calories per mole30 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Zone I (g) (350°-1,000° K.) Cy=23:344-2,30% 109 T—3.60% 1057-4 (83) Hy Hoa 1 SADE BBIATH LIB 10974380 xaert Formation: C+2Cl———>CCh, Zone I (350°-1,000° K.) ACp= 1.64 1.16% 1037— 0.14% 1097-2 27,020-+1.6T-+-0.58% 10° T?-+0.14 1057 = 27,020— 1.6 Tin T—0.58X 104 T7+-0.07 X10 44544 ox, Esasseze asusuer’ Carbonyl Chloride (Phosgene), COCI (9) = meat ,300 calories per mole (112) 15.34 K a8) 371 ealories per mole 80.7° K. ($8) 5,825 ealories per mole Zone I (9) (298°-1,000° K.) C,=15.6043.46% 10-97 —1.91 x 1057" (82) Hy—Hyo= —5,446 4 15.607 + L73X 10-9724 1.91 xa Formation: C+1/20,+Cle COC, Zone I (298°-1,000° K.) =0.90-+1.88% 10°74 1.07107 = 52,700—0.907 + 0.94% 10-972 1.07 x107 AF r= — 52,700 +-0.907tmT—0.94x 10-*T*—0.54 XIOT 43.027 | SEEREERERY 1,430 calories per mole 303° K. (82) 950 calories per mole 463° K. ( (9,700) calories per mole Zone I (a) (298°-320° K.) 45 (82) 287 4-34.57 ¢, Hr Hw Zone II (8)(320°-363° K.) y= 48.0 (82) Hy—Hyg=—11,580+43.07 ‘Zone III (2) (363°-463° K.) ¢, Zone IV (9) (463°-1,000° K.) y= 25.08+0.60% 1073.03 10°72 (82) Mey Hon =5 200 25.087°+ 080X097 3.08 Ser Formation: C-+2Br;————>-CBry, Zone I (298°-320° K.) 3.8—1.02X 10° 7$2.10X10°7T-* 877—$87—0.51X 10-97? 2.101097 877+ 387m T+ 0.51 X 10-7? 1.05 dO 10.17 Zone II (331°-363° K.) 86— 1.02% 10-97+2.84< 10°T? 0,000+ 20.86 70.51 X 10-97 —2.84X 1007+ 20,000 20.86 Tin? 0.51 X 10-9 72— 1.42 X17 20107 Zone IIT (363°-463° K.) 14.55—1.02X 1097+ 2.84X 10°72 180+ 14.557—0.51X10°7 2.84 16,730— 14.55 7In T+ 0.51 10-972 1.42 X1OT 4 15427 Zone 1¥ (463°~1,000° K.) ACy=2.80—0.42X 10-°T—0.19X 10° 7-* BHy=—3,310+ 2897 —0.21X 109 T°4.0.19%10°T* ‘AP p= —3,310—289TIn T+ 0.21 1047+ 0.1 X1OT 4 52.97 BESSSE8 ie | nes) Carbon Tetraiodide, Cl, (¢) (39,700) calories per mole (11) (60) eu. (1) 44° K. (6) 1,150) ealories per mole (580°) K. (6) 12,000) ealories per mole Formation: C-+-21,————>C, (estimated (11))HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA i ox, Hr-Hm | ant are Sis] Sa Cyanogen, C:N: (9) Hin =73,000 calories per mote (112) ls ‘Sig= 57.86 e.u. (112) MB aH 12) bee K, (112) ‘ify=5,576 calories per mole Zone I (g) (298°-2,000° K.) 14,90+ 3.20% 10° T— 2.04 10-°T-? (82) 70-4 14.907 + 1.60 10-272+ 2.04 x10 Formation: 20-+-N;————>C:N, Zone I (298°-2,000° K.) AC,=0.04 40.14% 10° T+2.16 x 1097-4 AHy=74,250+ 0.0474 0,07 X10-*T2— 2.16% 108T1 ‘AF7=74,250— 0.047! T—0.07 X 10-°T— 1.08, X10 = 10.457 ox | unm | 5 | ae m. | 4z.00| 4190 Be ee) “22 “28 & Se) Rie] ee fe) Rie] eae Re) | SS a BH 5h] tee Ht Bi} 13s) Sie HB Re] 3D] geo EBS Bal Ham) She EB BS) ii) Sie Ba fe] 2B) EB L800. em 0 18,400 tee Ba; | Sie ipo Sa) RS) Bie Yeo Bel | Bie 3 BE) 3) Bs Cyanogen Chloride, CNCI (9) ‘Alfye=34,500 calories per mole (112) Sait Sl ou. (ie 6.3" Ke. (112) ,720 ealories per mote 86.19 K. (112) 200 ealories per mole Zone I (g) (298°-2,000° K.) Cym 11.884 1.64X 10-97 1.49% 107 (82) Hy Hm SUB MLSE 082K IO LAD Formation: C-+1/2Ch+1/2Nr CNCL Zone I (298°-2,000° K.) 04 0.08% 10-97 + 0.95% 1007s 4,800 -+0.047+0.04x 10->T?— 0.95% 10871 Loan 004x109 T—0.47 & 26, a} 34500] 90 ‘to. S| 3t's00| am i: | ete | Stam ‘ae. | Mito att ‘in, fo] e000) Sag S- 3) 3¢80) ao ‘na, | aeeea | a0 1006, fo| 3¢80| ato ta Sto] ico Tate. @| Seo | 2800 0. | om | Zoo) F400. te Senso] Zea bep0 es Shes) 3800 0. S| 34000) Bom 00. S| dea] 3000 Tao | See | Bam ‘0 | suo! Bi Eis a | 3e060| em Cyanogen Bromide, CNBr (/) @ X10" T4134 Formation: C-+1/2Brs+1/2N;——>CNBr Te, Heat | Se ERERGEEESESE apseageeeseee seeuensesense — Cyanogen Iodide, CNI («) ‘AHia=40,400 ealories per mole (112) B08 eu. (112) 418° K. (112) 14,200 ealories per mole Zone I (g) (413°-2,000° K.) Cp 12.804 1.88X 10-97 1.04 10°7 (82) Hy— Hox = 10,100-+ 12.807 + 0.60 10-9 72+ 1.08 xin Formation: C-+1/2N,+1/2l——>-ONI. Zone I (456°-1,500° K.) AC p= 0.43 = 0.15% 10-* T+ 1,06 1057-* AH = 47 450+ 0.43 7— 0.075 x 10-47 1.0810" ‘AF -=47,450— 0.43 Tin T+ 0.075 X10 7*—0.53. X1OT 7.0732 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS ce laewa) me ce Dicerium Trioxide, Ce. (¢) em lib aa 000) ealris per mole (#4) a ery se net en (ee & wee) He ei Me. ua) & ee) ae se st | age) Bo Be Formation: 2Ce+3/20,——>Ce,0, ia ge) Be ea (estimated (24)) 13 Be| si ino oo. a) Re Sin ‘is Site | au 2000 in| Sit eis a. & es +100 goo Beco +00) 8 Veto ad yoo F eo — 1iso. — = ip & sao} ge, ee | 4 te cnn Be ea Rigo a oe a 2 E pope Po] oo 2 co Cerium Dioxide, CeO; (c) 8 00" — 260,180 calories per mole (68) 8 oh 14,88 eu, i, = -60) 5 = >2,873° K. (42) & 40) Zone I (@) (208°-2,500° K.) B oh ne 15.042.5X104T (94) cd — i" 4580+ 15.07+1.25% 1097 5.20 < Formation: Ce-+Oy CeO, 140} Zone I (298°-800° K.) a0 B00 44—4.50%10-*74.0.40% 1057-# ° 250,500-+3.447—2.95%10-*7"—0.40% 10°71 eee 259,500—3,44 Tin T+ 2.; E10 0.20 Fravax 10—Carbon. IOP 69.257 CERIUM AND ITS COMPOUNDS — Eo Pale Element, Ce (¢) Sooo cw ee 12) ye) Be a) iB] 22 120 eslories per atom (112) S| Re Zone I (c) (298°-800° K.) 23) Be €p=4.404 6.00% 107 (82) | Be | aR 1,575+4.407+3.00% 10-97? 40Tin T—3.00X 1097+ 17.657 = 1575 =| ox. Hr-Hu | & |-G Cerium Trifluoride, CeF: (c) — 391,000 calories per mole (6) 24) eu. (11) 4 w) bel Be < 1 Bi i 1,703") K. (29) fig) a] ter 9,000) alories per mole dim! ik) ik '2,600°) K. (6) iB a af (22000) ealories per mole B 3) fe Ey a 3 Formation: Ce+3/2F;———>-CeF, (estimated (11))HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 33 mm [tim | um | om 2 ~eel ce Besos coal Bi] ae Bec) gy a ee 00. SSIS 88 50) = 307, Cerium Tetrafluoride, CeF, (c) ‘Alj= — 442,000 calories per mole (11) Ja 89,m (1) MP.=(1,250") K. (6) ‘AiTy= (10,000) calories per mole Formation: Ce-+2F;_——=>CeF (estimated (11)) Cerium Triiodide, Cel; (c) 168,000 calories per mote 6) (50) e.u. (11) |,038° K. (29) 000 calories per mole 1,670") K. (6) (40,000) calories per mote Formation: Ce+3/21,——>Cels (estimated (17)) mx | teatim | ate fa =| ae we as +40) p B +60} =z Cerium Trichloride, CeCls (¢) i a 4 +80} |____ fava" | 252,840 calories per mole (128) s st ee i ($,000) ealories per mole 24 21000") K (6) & 6,000) ealories per mole 5240} Formation: Ce+3/2Cl——>CeC, § 60) (estimated (f1)) © ed} ene 200) a § -s2q © sad =e E -se0} <_ - cay Are 5 380} 7 09 AF — — 192,000 calories per mole oe al a @ ae 300 500 1 208 ez eu. (11) MP. Le Ke) 3 a ole BB Se on Formation : Ce-+3/2Bm——>CeBry, (estimated (11) He-Hin | ante are TEMPERATURE, *K. Fioure 11.—Cerium. CHLORINE Element, Cl: (g) So=53.31 6.1, (83) 172.168 K. (112) 1,531 calories per atom P= 259.1" K. (112) ‘Aify="4,878 calories per atom34 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Zone I (g) (298°-3,000° K.) 8240.08 10-°T—0.68x 107-482) 2,861 48.827 + 0.03 X10°77+0.68 xia Fete “Bg so7igT 00010-4034 parce vetm | me | est al gs 2) #) OB ig] #2] #8 ig] §B) #8 ig) sf) Be ig) Be) Bg ig) fe) ES ie] Ha) a eee) Be S| oH] ea : ge] 8 is] a : ae] 8 an] 8 a3] CHROMIUM AND ITS COMPOUNDS Element, Cr (c) 8 en, (83) Ts Tia Zone I (e) (298°-1,800° K.) Com 5.84-4-2.30% 10-7 —0.88X 106T-* (82) Hy Hyg = 2140+ 5847 +1. 18X 10°74 0.88 1071 Fr—Hya= ~2,140~5,84TInT—1.18X10-°T?+ 0.44, X1O6T34.567 “| im | = al 2: foe] tel = Bl & 1B] iB) ie = 1B) om) = ==) #8] ga) i = iB) oat] ot i He) i) ia ao iS) Hig ao iB) iz ig) 2) Re igo ig) i) Rs ig te) ms) ie iS He) ORR) gg ES He) Re) gs a RB) BR] BE 272,650 calories per mole ( Siss= 19.4 e.u, (112) " ° Zone I (ec) (298°-1,300° K.) Cy=28,58-+2.20% 10-°T—3.74x 1087 (82) Hr Hon 9100285371 10XIO"P 3.74 Formation: 2Cr 3/20,.——>Cr,0s Zone I (298°-1,800° K.) AC,=6.11—4.02X 10-97 1.38 1067-2 =274,750-46.11 2.01 10°74 1.38% 1087! = 274750—~6.11 Tin T+2.01 X 10° T° 4-0.69 10714 105.957" [eum] oe | ae a | gs) ee) ee Beccccchgy| 26) ee) ce 2 a8) Ge) HS) Be a i) 22) 28) 28 # ig) Be 3 sc] ee) Bs] aR) cee Be S| 28) 28) (Be ‘s £8) 22] 228) cae a Pre es S ae oe ‘ Pe Te ie ae oe ‘e Sa) 88) -2e) 88 ig Se) $8) CrO, (estimated (24)) seey (Si 0 135,00)HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 35 Chromium Difluoride, CxF, (¢) 182,000 calories per mole (11) 5 x 10,000) ealories per mole Formation: Cr-+F,———-CrF, (estimated (11)) 40) (aos) Cis sy 0) Gp] i iat) : Grows] Cisse) Casta) | ae 266,000 calories per mole (112) 5) eu. (11) ‘373° K. (6) 1,000) ealories per mole 700°) K. (6) 8,000) calories per mole Formation: Cr+3/2F,————>CrF (estimated (11)) = 286,500) calories per mole (11) 18) eu, (11) 350°) IK. (6) 500) calories per mole 370°) K. (6) 14,000) calories per mole Formation: Cr+2F;———=CrF, (estimated (11)) 94,560 ealories per mole (112) 7.8 eu. (83) 088" K. (112) Zone I (¢) (298°-1,088° K.) 0y=15.2345.30% 1097 (24) Hy Hya= 4,770 15.287 +2,05 10-97? Zone IL (J) (1,088°-1,573° K.) C,=24.0 (04) Hr-Hy Formation: Cr-+Cly Zone 1 (298°-1,088° K.) 57 + 2.88% 10-7 41.56% 10°? 94,830-+0.57 T+ 144 10-*T2— 1.56% 10°71 94,330 —0.57 Tin T—1-44X 10° 7?—0.78 X14 34087 Zone II (1,088%1,573° K.) 134 — 2.42% 10-47 4+1.56%10°7-* ‘92,900-+9.347— 1.21 10-*T?— 1.50% 1087-1 92,909.34 7in T-1.31 x 10-°7*—0.78 X10 90.877 =3,400+24.7° CrCl, ™ BB | | ng =: rie # ve) # iB) Bg ‘0. - | Tas) aoe Be ig] is Bag) AM) BS yo S| aaa |e | = | Ba) # i 8) 3] icc] BB) BE) Chromium Trichloride, CrCl; (¢) AH i= — 132,500 eslories per mole (94) Sya= (30) e,u. (88) 1,220" K. @) 58,800 calories per mole Zone I (¢) (298°-1,200° K.) (p= 19.44-47.08% 10-47 (94) Hy—Hyn = — 6,105 19-44 7+3.51 1 Formation: Cr-+3/2Cl,———>-CrCl ‘Zone I (298°-1,220° K.) AC>=0.37-+-4.58X 107+ 1.90% 1057? 132,300+ 0.37 7+ 2.29 10-*T*— 1.90% 10°T* 132,300 —0.37 Tin T— 2.20 X 109T—0.95 1074 58.007 EER ene | BBeeeEs:36 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Chromium Tetrachloride, CrCl, (0) Formation: Cr+1,——Crly (estimated (11)) AH4=— 110,000 calories per mole (11) Cr+2Cly———CrCh, (estimated (11) mmm | at | an Tetrachromium Carbide, Cr.C (0) 16,400 eslories per mole (112) 5.3 eu, (112) B= 1,198" K. (98) Zone I (¢) (298°-1700° K.) Cy=20:35 47.40% 10-*7'— 5.02% 1057 (82) Hy Hop — 10,764 20.357 + 3.70% 10-*T?+ 5.02 (—74,000) calories per mole (11) x 10T tise KO) ormati a 5.300) along per mole Formation: 4Cr-+C———~Cr, 38,000) esiowes per mole Zone 1 (208°-1,700° K.) 1,893.06 X 10-*7+0,60% 107-4 =16,620+1.897— 1.53 10-*7*— 0.60% 10°T-* = 16,620— 1:80 Tin T+ 1.53 10°7?—0.30 X1O'T+ 10.197 Formation: — Cr+Br;———~>CrBry (estimated (11)) 38) Bie im) Re in| Be im) 88 ime) iat Em] at ga) ae 91,000 eal ole (11) Sito | Be aa) eu (11) dap] Rit 12068) Ko) gio] ie 54,000) calories per mole gin] a8 + Cr43/2Br————>CrBr (estimated (11)) Heptachromium Tricarbide, Cr;C; (c) 42,600 oalories per mole (112) ‘Siw =48.0 eu. (112) Disproportionates 1,940° K. (8) Zone I (¢) (298°-1,500° K.) Cy 50,06 + 14.54x 10-7 — 10.12 1087 (82) Hy—Hoa=—21,010-$ 56.967 +7.27X 10-7? + 10.12 xi Formation: 7Cr+3C-————~-Cr,C3, sath, exo por mate (12) Zone 1 (298°-1,500° K) eric Te S04 10-TE 298x107 (6,000) calories per mole 12,600 + 3,78 1—2.52 X 10° T?— 2.34 x 108! 1,100") IK. (6) Py —42,600—3.78TIn T+2.52X 10° T— 117 (24,000) calories per mole X14 18.307HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 37 Hr ark a. 0 a s i ie Sd & ed Si oe Set 30 xo: igen | =ee0 a id a St by iB Ft 0 =a ho 7 =a Trichromium Dicarbide, Cr,C; (c) Hix 24,000 calories per mole (11 Spnaoden Gy Pe mae GP MB DG (ite) Zone I (c) (298°-1,700° K.) Cy=26.194.9.48% 10-97 4.721057" (8f) Hy— Ha= —9,790-+ 26.19 744.74 109TH 4.72 x17 Formation: 3Cr-+2C———~>Cr,C, Zone I (298°-1,700° K.) AC,=0.47 +0.36% 10° T4212 107-2 AH = —20,450-+0.47 740.18 10-°T?—2.12% 1057 SF p= = 20,450—0.47 Tin T— 0.18% 10-°7*— 1.06 x1 +1407 SS en tthe \ K ‘roy AF, FREE ENERGY OF FORMATION, keol./g, —mole 300 500100 TEMPERATURE, * Frovre 12- 20 S48 . __— 2. gfe obs F ceoh [Lecce ob 3 ome $ sof sete Fol AE - 2 azo — 3 al 8 ood 2 za & -240} = 5 cn PF Cr:N Zone I (298°-800° K.) 87 + 1.08 10° +-0.88 10°T-* 19.450+0.67 7 +-0,51 x 10° T*— 0.88 10° 29,450 0.67 Tin T—0.51 x 10° 7*—0.44 X10 T+ 23.96738 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS ol COBALT AND ITS COMPOUNDS Element, Co (c) 8c. (83) i calories er stom 400" Ke. (a2) 30 ealories per stom abs Ke (32) 240 calories per stom 337° iD Zone I (a) (298°-718° K.) 724430X10-7 (82) STiao 279.18 %10-47 <0 727m Te 10% 10-9425 047 30+5.86% 10-7" (82) =979F3.307 42.93 10-°T? =979~8'307In 2.93 10-974 16.367 Zone TI (7) (1,400°-1,763° K.) * ©,=9.60 (82) Hy— Hon = ~3,920+9.607 '7— Hon = —3,920—9.00 Tin P+-60.07 Zone 1V (2) (1,7639-1,900° K.) 8,30 (82) +2,010+8.307° $2,010-8.307mT+47.077 Hr-tim |S | (Pr Hw) 57,800 calories per mole 2.63 e.u. (38) r g ore. (are) Zone I (c) (298-1,800° K.) Cy=11.54-42.04% 10-7 +040 1087-1 (82) Hy—Hyam= ~3,400-+ 11.54 T+ 1.02% 10-97?—0.40 xaor Formation: Co+1/20,—— Zone I (298°-718° K.) C00 —57,940+3.247=1; = 57/940—3.24 Tin T+ 1.38% 10-*T?—0.30 X14 39.287 Zone II (718°-1,400° K.) 4.66 4.82 10-°T 0.00% 1067 58,500-+ 4.68 72.16 10-*72— 0.00% 10°T-t = 58,500— 4.66 7In T+2.1610-*7—0.30 X14 48.07 Zone IIT (1,400°-1,673° K.) LOL 1.54% 107+ 0.60% 10°74 55,750— 1.647 40.77 10-°T2— 0.60% 10°71 — 55,7504 1.64 Tin T—0.77X10*T?—0.30 XIOT 8477 Zone IV (1,673°-1,800° K.) 0.34++ 1.54% 10° 70.60% 10° 61,480—0.347-+ 0.77 X 10-°T?— 0.60 10°T-* 614804 0:34 Tin P—0.77 x 10° T?—0.30 X1OT HT eheeeeeeupene: Rageeeuenaees! Tricobalt Tetraoxide, Co,O, (c) —207,000 calories per mole (24) 15.66 eu. (24) Zone I (¢) (298°-1,000° K.) 30,84-+17.08% 10-97 5.72 10°74 (91) 11,8705 30.847 +854 107724 5.72 x1OT Formation: 3Co+20,———+C0.05 Zone I (298°-718° K.) SC ,=2.36-+ 218X 10-97 — 4.923 10°72 "209, 450-F2.367-+ 1.09 10-*T2+-4.92 x10T* 209,450—2.367In T— 1.09 10-97? 2.46 X1OP 4102167HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 39 Zone II (718°-1,000° K.) Zone I (c) (298°-997° K.) 6.62~2.50X 10-9 T— 4.92% 10872 441-4 14.60% 10-7 (82) 211.200-40.627—1.25x 10-4 4.92 Hey— Hyg= 4.9454 14.41 747.30 10-472 x10 111,220— 6.62 Tin T+ 1.25 10 T?+2.46 Formation: Co+Cl-———>CoCl, X1OT14131.037° Zone I (298°-718° K.) 187 + 10.24 10-9 7-+.0.68% 1087 = 78,3004 0.877 +5.12X 1070.68 x10 “78,800—0.87 Tin T— 5.12 10° T—0.34 X1OT 44337 Zone II (718°-997° K.) AC, =2.29+8.68% 107+. 0.68% 107-4 ~79,000+2.297+-4.34X 10 72—0.68 X1OT 79,000—2.29 Tin T—4.34X 10-* 720.34 X1OT 453.027 Cobalt Difluoride, CoF, (c) 158,000 calories per mole (11) aan tayo moe aD 14759 K. (6) (G,000) calories per mole (20009). (@) (48,000) calories per mole Formation: Co+F;———>CoF (estimated (11) 2228258 5 : wt Hg — 50,600 calories per mole (11) | te-tim | ane a ‘Sig (33) eu. (11) om MP. iy (6) al ces ce Miy= (8000) cloves or mole a8) CES) CES = ako SS) CES) CE is 0800 Sirs pr mate Formation: Co+Bry —€0Br, (estimated (17)) Cobalt Trifluoride, CoF; (c) BK, trtin | ane | aPh per mole (11) FE Fe ma ol ap BAS cpa 10) ® = ‘eiom) ify (40,000) eaiories per mole Formation: Cot 5/2 ———-+CoF, Cobalt Diiodide, Col, (¢) =21,000 calories per mole (11) (37) eu. (11) 790° K. 6) (6,000) ealories per mole (1)100°) K. (6) ‘4, = (24,000) ealories per mole Formation: Co+I,- — Col; (estimated (11)) eis) von) Cobalt Dichloride, CoCl, (c) ar AHie= —77,800 calories per mole (112) Sen ded eu. Gay Pee mole (118) a 90) MEARE Up er ‘Sig =7,A00 calories per mole Ser Lees y ‘eked ‘AHy=27,200 calories per mole40 THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Tricobalt Carbide, Co;C (c) ‘AHin= +9,830 calories per mole (81) ‘Sine= 22.8 eu. (9) 9,000 ealories per mole Columbium Dioxide, CbO, (c) (=10,400) calories per mole (24) ‘Siu 13.03 e.u. (91) Formation: Cb-+0,———>Cb0, (estimated (24)) Hatin | aa- fe amr | apes q e afer] Bi F 20h cw <—-| 2 e a m Sud | = 5 [ee 1s. oe e [eel 18s § 8) 18. % / Yo & soo} eary| 20 2729 Dicolumbium Pentaoxide, Cb.O; (¢) 8 so} | 5 x60} = BP.= >2,500° K. (42) Zone I (¢) (298°-1,785° K.) 180) 5=86.23+ 5.54 10-°7—4.88% 10°74 (102) eee cer 00 POO Hy — Hen =~ 12,680-+ 36.287 + 2.77 X 10° T+ 4.88 TEMPERATURE," Fiaure 14.—Cobalt. COLUMBIUM AND ITS COMPOUNDS Element, Cb (c) Tew. () (6,500) calories per atom BBR annie ‘ity =(155,000) calories per atom Zone I (c) (298°-1,900° K.) 6.0.96 %10-7 ($2) =1,730-+5.667-0.48% 10-472 =1,780= 5.667% 7048 10-972 4-29.45 xa0'r Zone II (2) (1,785°-1,810° K.) C= 57.90 (107), Hy—Hoa=— 17,2554 57.007 Formation: 2Cb+5/20,——>Cb.0s Zone I (298°-1,785° K.) AC,=7.014 112X109 7—3.88X 107+ 458,440 7.01 T+ 0.56% 10-972 4.3.88 10°7-* = 458/440 7.01 Tin T—0.56% 10-972 + 1.94 X10 14 156.527" ‘Zone II (1,785°-1,810° K.) 28,684.42 10-87 +1.0% 1087-2 163,750 28.687 —2.2110-*T?— 1.0% 1057-1 463,750— 28 68 T!n T'+-2.21 x 10-*T?—0.50 X1O1+ 317.07 7x ; atl = 2a | cee) as iw) 8h) gw} Bh) $08) aS : ig; & ig) = 2 =} x) = a8) ER 3 : kin| Eig s ig | Bas = ig} ie eel 88 2 con ER] eg Bocce Be) ae 2 : ig) i a ae) 38 3 iB] tk ie ee) Bt 2 : is) Oe 2 ae) Gh 2 ig) Re ‘2 #8) 22 | iB) ke 2 ee) 28 3 is) ‘s Be) ee & ie) Hote iB ie Be 2 =| #2 asl iB es BS 2 Ss) dt) ah) aS) BS) 3HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 41 Columbium Pentachloride, CbCI; (c) AH?3= —190,600 calories per mole (48) Sye= (65), ex. (11) 485° K. 8,400 calories per mole 516° K. (6) 11,500 calories per mole Formation: Cb+5/20l-——>CbCl, (estimated (17)) mk. | teattm | an | art | abs ‘0, iste) Columbium Pentabromide, CbBr; (c) AH?y3= 182,850 calories per mole Spa (78) eu “ 500° K. ( (22,000) calories per mole Formation: Cb-+5/2Bry————>CbBr,, (estimated (17)) | ane | ane ari 1p. 0 | (126 299 (08 $05) (E1030) 56,800 calories per mole (100) 0.5 eu. (9) B72 K. (94) 14,500) calories per mole Zone I (c) (298°-600° K.) 8,694.5.4010-7 (94) 2,831 8.697+2.70X10-°T* CbN 3043.93 % 10-97 ,900— 0.307 + 1.98% 10-97 ‘AF p= — 56,90040.30 Tin P— 1.96 10-972 + 20.427 19K. Hr-tim| sr | ant | are 9, T "1 3 f \ AY \ 3 AF, FREE ENERGY OF FORMATION, keol/a. -mole 360) omg "300 1000 TEMPERATURE, °K, Fraure 15,—Columbium. COPPER AND ITS COMPOUNDS Element, Cu () 91 a4, (9), ‘Bifp= 72,800 calories per atom Zone I (¢) (298°-1,357° K.) AL 150X107 (82) =1,68045.417+0.75 10-87" = 1680 5.41 Tn T—0.75X 10-4 28.77 ws | See8888 ‘bo. ‘aia in is a He) Hg) a HB) ke! ke ‘io. fio) ise) net Wi to ike Le 0 sm) Re) nS Be ue) Bal BE is ae) ES) gS is Hes) Bal BE to He] RS) BS Bo aS) Gk) a is S| ib) fe ton 3) ee ee i30 ass) GS) ate42 ‘THERMODYNAMIC PROPERTIES OF 65 ELEMENTS Dicopper Oxide, CuO (¢) Copper Fluoride, CuF (c) 60,000 calories per mole (11) 6) eu. (11) 020°) K. (42) ‘Ss MP1 go" Gy fi ‘AHy= 13,400 ealories per mole AH y= (4,500) calories per mole B.P.= (1,660) K. (42) Zone | (¢) (298°-1,200° K.) ‘ay = (88,000) eslories per mole ym 14.904.5.70X 10-87 (82) oa Hy Hg 800 AMPERES LOT Econ edt ae Formation: 2Cu+1/20;——>Cu,0 Zone I (298°-1,200° K.) ox, Hr-Hm | Sr SEuBEEH Formation: Cu+F;——>CuP, (estimated (12) 3 22BEsseesaveny ssesseensacss BEER 37,500 ealories per mole (2) Squ=10.19 eu. (98) = 1,720" K. (24) ‘AH y=2,820 calories per mole Zone I (c) (298°-1,250° K.) = 82,600 calories per mole (11) 0.8 eu. (83) 108° KK. (82) 9.274. 4.80% 10-7 (52) 620 calories per mole 29779277 + 2.40% 10-87? 963° K. (6) + Cut1/20y cuo 31,600 ealories per mole Zone I (c) (298°-703° K.) 2_1.950° 87 + 19.20% 10-7 (82) AH t= —37,640-+0.287+ 1.4 10-9T2—0.20%10°T Zone II (I) (703°-1,200° K.) < 37/540 0.287mn 1.4% 10-97-0110 X10 24037 Formation: Cu+1/2Cly Zone I (298°-703° K.) = 954-17.67X 1097 -40.34X 10°72 = ae ge Saar e wasiOe O34 a iis X10T = | or AF =" 31,066-+3.957InT—8.83X10°7?—0.17 a io | Bae X1OTIA 7.567 vio Re] RE Zone IT (703°-1,200° K.) the Ia drs 5 i : 0~1.58X 10-47 +034 1087-2 Ya. tea st Sa4800-F8.07 0765x101 0.34 a a6) ES We conarsorexurer 0 X1OT 4-50.57)‘HEAT CONTENT, HEAT-OF-FORMATION, AND FREE-ENERGY DATA 43 se | ant ma) mae RL) BS. Re] 8 a2) 338 Be) aes 82) iia | a G8) RS Copper Dichloride, CuCl, (c) Fle —58,400 calories per mole (11 yay tay Por mole 1D Detomposes._ 810" K., 1 atm Cl (6) Zone I (¢) (298°-800° K.) Cy= 15.42 + 12.00 10-*T (82) Hg 51 FDOT EOD IO Formation: Cu-+Clh——>CuCh, Zone I (298°-800° K.) 119-4 10.44% 10-174 0.68 x 1007-2 Log ovo Liars 5 22510-T— 008x107 = 53,990— L197in T— 5.22 10° 7—0.34 x04 45.07) ne, BBbRRE 8a88g8 —25,450 calories per mole (11) 2.07 eu. (55) 761° K. (8) 2,300) calories per mole 591° K. (6) (33,400) calories per mole Formation: Cu+1/2Br-——>-CuBr (estimated (17)) | rtm Copper Dibromide, CuBr; (c) AHin= —33,200 ealori Sow 3) eu, 11) Decomposes—600° K., 1 atm Bry (6) per mole (112) Formation: Cu+Br,p———>CuBr, (estimated (11)) Helm | ant BIR = wii, HBG) Copper Iodide, Cul (¢) BE 1480" K. ©) ‘AHy= (81,100) eslories per mole Zone I (¢) (298°-675° K.) 2.142.86X10-7 (82) Hp— Hon = ~3,788-+ 1217+ 1.43 X10-°T? Formation: Cu+1/2l,——>Cul Zone I (298°-386.1° K.) 9459x1047 =16,850-+1.97—2.20% 10-72 16,850—1.9Tin P+2.29X 104 T+ 9.477 Zone I (386.1°-456° K.) ACp=—2.9141.86X 10-7 aHy= —17,350~2.917+0,68X 107° ‘AF p= —17/350+ 2.91 Tin T—0.68X 10-97 16.17 Zone IIT (456°-675° K.) ACp=2.2141.36X 1097 AH r= —24,700—2.217+-0,68% 10-*7 24;700—2.21TIn T—0.088X 10° +31.37 (estimated (11)) ay He-Hn| S| ane | are mL is] Bae em | ae fom) sat Cixgo| {ano Tricopper Nitride, CusN(c) 17,800 calories per mole (9) Metastable, decomposes >740° K. Copper Nitride, CuN (c) - —60,230 calories per mole (181) “62,850 calories per mole Copper Trinitride, CuN; (c) ‘AH =67,280 ealories per mole (48)

Thermodynamic Properties of Elements Their Oxides, Halides, Carbides and Nitrides

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Thermodynamic Properties of Elements Their Oxides, Halides, Carbides and Nitrides

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