High Temperature Proper s and Decomposition of Inorganic Salts Port 3. Nitrates and Nitrites Kur H. Stern Electrochemistry Branch, Naval Research Laboraory, Washington, DC: 20390 “The lterature dealing wth the hightempersture behavior of inorganic nitrate and nites has been etically reviewed. Values of (C}~Hfq)T ofthe reactants and products ofthe decompasiion = were clelated an ha Equi constants aad part densities have als been included. Quali reviewed Key words: Nitrates tite; thermal desompos heen ahead frm 298 Ku nas hh a tmneratare as vom presses mere tabulated. Auslary data on phase te ine information about the thermal decomposition ofthe salts re and ‘hermodynanic fonctions Contents 1, Introduction 47 Lithium.. 759 ‘Symbols, and Abbreviations... ‘3. Gaseous Equilibria tn the N-0 System. Chromium Cobalt. 1, Introduction During the past decade or two, inorganic salts. par- ticularly in the liquid state, have assumed increasing importance in a variety of applications. They are useful as reaction media, in metallurgical processes, and i electrochemical power sources such as fuel cells and thermal batteries. Experimentalists and theoreticians have found molten salts an interesting subject for study since these ionic fluids offer an unusual opportunity for the study of short- range ionic interactions in the liquid state. So far, attention in this field has largely been focused con the alkali and alkaline earth halides since their stability at high temperatures is well known, The most ‘orteh © 172 y the US Suey af Como al fe Ud Sta ‘Magnesium .. 761 Manganese: ra Mercury... . 762 Nickel socsecnsssentenessne Palledioon 769 Polonium. Potassium... 762 Radium 64, Rare Earths 708 Rubidium . 165 Scandium + 166 Silver, + 766 Sodium 167 Strontium ‘Thallia. Tin Titanium .. Zine Zirconium. . _™ ‘Acknowledgements, ™ References, ™ important decomposition which they can undergo is dissociation to the elements. The extent of this dissocia- tion can be easily calculated from 15 thermo dynamic compilations, For most inorganic salts the situation is more com- plicated. In many eases the decompaition reactions are not well defined and high-temperature thermodynamic and kinetic data are either lacking or scattered through the literature. Thus, although many of these salts have useful properties, they have received little atten- tion because in many cases not even the range of thermal stability is known, The purpose of the present publication isto alleviate this situation by publishing in concise form thermo- dynamic and kinetic data relevant to the high-tempera- ture behavior of important classes of inorganic salt. For the present, data in this work are restricted to anhydrous compounds with monatom id evyanions sontaining ne alana Ine onveon 4. Py. Cham. Rat. Dat, Vel 1, Mo. 3.1972m8 kuRT H. In the preceding two volumes dealing with carbonates and sullates, respectively, it was possible to calculate thermodynamic functions for the decomposition reac tions of many salts because (1) the reactions were well known, and @) heat capacities for the salts and the Accomporition products were known. Moreover the composition of the gas phase is simple in both eases: CO; for the carbonates, and the single equilibrium S0,=S0.+1/2 Os for the sulfa ‘The situation with respect to nitrate decomposition is diferent: (1) Many nitrates, particularly those of the transition metals, have only recently been prepared in the anhydrous state and very litle is known of their thermal behavior, (2) The decomposition of the alkali ‘and alkaline earth nitrates first proceeds to the cor- responding nitrites. ‘Over certain temperature ranges nitrates and nitrites may be equilibrium. Therefore these two groups of salts are tr ed in a single volume. (9) The course oft sions is aot wel understood. The gas phase composition is complex and may contain Oe, Nz, and several oxides of nitrogen. All of these gasco may react with tho calte and each other, reversibly or irreversibly. The course of the «decomposition thus depends on experimental conditions. (@) For very few nitrates are there any thermodynamic data above 298 K; for nitrites there are virtually none. ‘The procedure that has been followed represents a compromise between total reliance on thermodynamic Compilations on the one hand, and experimental data om the other. When experimental studies exis, these are discussed and, when possible, used inthe calculations. When no experimental dats about the deeunpositivus exist, the thermodynamic data are used to calculate equilibrium constants and partial pressures for the reactione that probably occur. Since knowledge of the gas phase properties —Nz, Os, and the nitrogen oxides — important for these calculations, these are discussed in a separate section. Following the procedure estab- lished in the preceding monographs of this series subsidiary data on phase trans also heen listed. 2. Units, Symbols, and Abbrevi dyn em? T(K) = temperature in degrees Kelvin, defined on the thermodynamic scale by assigning 273.16 K to the tiple point of water (freezing point, 278.15 K=0°C) R= gas constant—8.3143 J mol! deg-!— 1.98717 ceal mol“ deg! H° =standard enthalpy AHP'= standard enthalpy of formation S° =standard entropy G° =astandard Gibbs energy fet G3 — Hits a free energy funet 4. Phys. Chem. Ref, Dato, Vl. 1, No 9, 1972, STERN ‘TGA =thermogravimetrie analysis DTA = differential thermal analysis 3. Gaseous Equilibria in the N-O System When nitrates and nitrites are thermally decomposed, nitrogen, oxygen, and their compounds are produced, A survey of the literature produces the following list of | substances which appear in one or another decomposi tion: 2, Ne, NO, NOs, NOs, N2O,, NzO5. Which of these substances are produced in any specific case depends on the salt, the temperature, and the experi mental conditions. Since rewet ns between these sub stances occur quite readily, thermodynamic functions for these substances and reactions between them have hoon lated sp to 1200 K. (Nitrates end i pose well below this temperature.) ‘There are two major sources for enthalpies and en- tropies: (1) the ongoing revision of NBS Circular 500, ‘Wagman etal. [Ib]lists values at 298.15 K; @) the JANAF tables (2] list these as well as free energy functions up, to 6000 K. The two compilations agree quite closely (cf. table 1) except for the entropies of NsUs and NoUs, a: though even these probably agree within experimental error. They represent diferent evaluations of the same data [1b}. For iuterual consistency we have selected the JANAF values. Free energy functions used in the calcu: lations are listed in table 2. Tables 3 to 10 lst thermody- namie functions for chemical gas phase renctions which ay occur during the decomposition of nitrates and ni- trites, To preserve differences, fel values in these tables are siven to more significant figures than the values at 298.15 K listed in table 1. This policy is the same as used bby [2], For similar reasons AHive.5 values are frequently, listed to more significant figures than warranted by the data. In these cases the uncertain digits have been sub- scripted. In listing thermodynamic values in joules ‘enough significant figures have been retained to permit recovery of the original ealones. ter decam- ‘Tapue 1L_ AU Pause and Saas fr some gases in the NO system SDF ater mel) | Slagle kag) cas — zs | sanar | 270-3 | JANAP N o ° wr | aszr200 0, o ° 8008 | 99.0001 No aist | asszoo | sose7 | s0ss7 Nos ros | taiz02 | 523s | s7a4x008 No, | 2001 | 2001 wo | 739105 Noo. 2 | 219 nw |az NOs 27 | 2teos | wo | me=10 Gas | APS wikd mol] | Sha wll wol"dee~) (2 ™ 191.50 o 205.03 No 210.55, NO; 29.90 Neds 300.26 NiO. 30828DECOMPOSITION OF NITRATES AND NITRITES m9 ‘Tans 2 Free energy fantions of gases,~ (6;—Hia)/T (J mol! des) m [ox o w | sm | sa | ma | xo wus | mse | sus | nase | am | sam | oman | sun me | ge | Be | hus] Sie | nae] Sate | Sime go | been. | dean | ten] Ss | ite | dae | Sit f | bie! | ae | eso | Sim: | ae | laa | Stas | mae | nee | ae | mz] sy | ae | mes o | gu | deat | dase | cm] Som | ewe | ae m | Be | iu | fico | Zee | Sam | Sua | Sug wo | gee | we | den | Stor | ems | mo | dees wo) mo | Be | me | se | Be | ee | me te | aus | ze | ine | Stas | Som | dao | Sita sori 0-80. _ sanitised ro | yas. | age | me | om | ae | ace fee] us | 220 | sesso | 0am | sox as |-nsas | ow | smo SS | cs | See | maak | Shea: far | Zam | tin | seu SU eee forse Sm | 82 | ER | ims | iss | Bios | far | chum | tos | ao S| came | Base | cine iar | cum | ote | 2% S| aes | Sat | Ss her | Gir | 222 | aie =t4 23H rw | at, | som | me | x sig | AE 3° | cise iach Sane so | Ziman soci tee fo | cian Pepi ius Be | cia uf tous is m tos ele ace 7 es iso | ies A voce On the basis of the data in tables 3 to 10.we draw the following conclusions: (a) NzOs is unstable with respect to dissociation into either NsOx or NOs from 298 K up. ‘Therefore it need not be considered in the dissociation of the salts. (b) The equilibrium NO«=2NOs shifts uarkedly to the right with increasing temperature, Above 400 K the concentration of NsOy is negligible. (c) Ab though NsOy has been reported as a product of nitrate decomposition itis unstable with respect to dissociation into NOs and NO above 400 K. It could therefore exist in equilibrium mixtures only near ambient temperatures. (@) The equilibrium NO+1/2 O2=NOs Is very tempera: 4 Phy. Chom. Rt. Data, al. 1.No 3.1072760 kunrH. cream, TABLE 7. NO. 2NO- TALE, NO,=NO,412 0, MMe 19.67 Kel, 57.1951 llip =~ 0.5 heal 2.29 rw | at, | acm | Wek K rw | act | soir | tok K s; a sieges | idee idee | Ider = ais | —oas | orem | ase | axexi0 zoa.is| —17550 | 6263 | -oa | Lax! oo | Seas | Tose | sao | 20x10 ao | asses | -a2ser | 42.256 | Lama so | —39.660 | —e1100 | 34a | 2.23% 108 soo | —asass | —ooase |" aase | Lance go | —so0er | enter | aarr | tevin oo | isis | Smmo | air | 13pm qo | —seaas | Tense | 3217 | 16x10 ro | -r73261 | ~o1356 | 47a | 66x10 am | 528m | esis | 3.166 | Lar x10 0 | —172522 | ~r010a | saz | 189 x10" vo | —sz21 | seme | sa | 192% 10 00 | —r7i6r2 | ines | S08 | 445i woo | 5671 | —émoa | am | ian %10. roo | =1roeas | unas | S536 | Resmi too | —sease | sea | sou | iano no | =170.030 | —n8035 | 616s | aa6xi0e v0 | 58856 | 52706 | aos | nonx ie 1200 | =198.281 | —i2nse9 | 630 | 2asa0 : | Tante 8. NO,+NO=N.O, TABLE 10, N.O,=N.0,+0, 0.548 kJ, — 9.690 heal 37:20 MJ, ~ 8.89 heal oe K K pei | ek K mais | unas | sac saaxie I ae.6n | as286 | 1.98% 10% so | stat | 29.952 Baixo 260.712 | assis | 4.13% .09 soo | arias | 60.100 721x104 -2si6s7 | i260 | sz x 108 eo | wos | 73300 Latx10-+ =22n'5i8 | aga | 855% 10% wo | moon | zat amo Haines | 4a | 270% 10" oo | nas | wis 20x10 J-aeo | mon } 110% 10% oo | ism | oxere roxio ow | ~1606 |-20538 | iors | 50x 10% wooo | 139553 | 99.010 615x104 wooo | 168.188 [200385 | 10.45 | 292% 10% noo | ages | 02.0 46x10 no | 12376 |-a96.9s | tan | mx 10+ 2 | assis | 05.107 324x104 wie [wee | roo | 115 10% ture dependent. Up to 500 K, NOs predominates mark edly; above that temperature both species are significant. ahile ane must always he con sidered in the salt decomposition. (e) Nz and Os are very stable with respect to both NO and NO; Thus, if Ns is formed during salt decomposition it will not react fur- ther. Oz may react with NO and with nitrites. () If all, equilibria were established quickly during decomposi- tion of the salts, Nz and Os would be the only gascous components. However, the reaction NOs=1/2 Ne-+Os is very slow below 1000 K. Thus, if NOs is the primary product of the decomposition it will not decompose ap- preciably by this reaction and only the equi NO+1/2 0:=NOy need be considered. For si sons the decomposition of NO to the elements can be 1d. The came conclusion war ronshed by Kelley examining the decomposition of a few nitrates. 4, The Nitrites Relatively little is known about the anhydrous nitrites ‘with the exception of the alkal metal and alkahne earth 4. Phos Cham. Ref. Dat, Vol 1, No.3, 1972 salt, The nitrite ion is less stable than the nitrate, so that the nitrites of magnesium and beryllium, small and hy charged ‘The nitrite ion is bent, bu there is still some disagree ment about the bond angle (116° or 132") and, the N-O distance (1.13 or 1.23 A) [63, 128}. Cotton and Wilkinson [89] describe the bent structure in terms of the resonance 6 on in MO thoory, by aastming that N forme threo sp? hybrid orbitals, one housing an unshared pair and the other two being used in « bonding to the oxygens. The be orhitale of N and 0) are used for a hond formation, ‘The coordination of the nitrite ion to the metal cation appears to differ with the salt. For example, in AgNOs, [Ag* is closer to N than to O, whereas in NaNOs, Na* is ‘loser to O than to N [63}. Since the metal ion-nitrite co- ‘ordination has not yet been much studied, the peri table of figure I which lists the known nitrites omits bonding antormation,DECOMPNSITION OF NITPATES AND NITRITES I Le [TBI SIN] OfF ine { iai/sil P| S [cia [criunle| (oes Selar Kr Te|Ru|Rh Joa Kalba in|Sn/Sb|Tel | Xe) Re Os| ir (Pt i /Po[at| Re LT) oye BE 68 THY. Ho Er TB Lu Tho U Np Pu AmCmBk Cf Es FmMd No Lw na Tol Fr Rolac Lonhanides etnies icine 1. Tha Nitstas: EN. exietanoe uncsetain, Nitrites decompose at lower temperatures than the corresponding nitrates. The course of the decomposi tion depends on the nature of the salt and the gas phase composition. Nittites of the more electropositive metals decompose to form the oxide directly by reactions of the type 2MNO:— M:O-+NO-+NOz, but if the gases are not immediately removed the nitrite is easily oxi dized to the nitrate by NOs, if the latter salt is stable at the tomperuture of the decemmpesition, In some eescey particularly the rare earth nitrites, the first decomposi tion product is an oxynitrite. According to Addison and. Sutton (20). simple nitrites will be stable only if a higher valence state of the metal is not readily available. Otherwise decomposition to oxynitrites will occur to achieve the more stable valence state of the metal. ‘This view is supported somewhat by the lack of exist fence of many nitrites of metals in the first two long periods of the periodic table (fig. 1), although the absence of Zn (NOs): is surpnsing. 5. The Nitrates Although anhydrous nitrates of the alkali and alkaline earth metals have been known and widely used for a long time, the anhydrous nitrates of many other metals have been prepared only recently. The existence of some is still in doubt. Methods for preparing these nitrates have been described by Addison and Logan {16}, ‘These authors (16a, as well as Field and Hardy (48a), have also recently written extensive reviews of nitrate chemistry. In view of these, only a brief summary of Uscrimal dewounponition is provided actin relevant here. Tn the hydrated salts and in aqueous solution the ni- trate ion isa distint entity. This is also true forthe an- hydrous nitrates of the electropositive metals, but in many other salts the nitrate ion is covalently bonded to the metal. The distinction between ionic and covalent nitrates can most easily be made on the basis oftheir infrared spectra. Chasan and Norwitz [36] have prepared a listing of ionie and covalent sold salts based on an ‘examination of the literature, and covalent nitrate com- plexes have heen reviewed by Addison and Sutton 20} Spectra of liquid nitrates have been diseussed by Ws and Janz (122) Figure 2 represents the author's evali- 71 Hi [Re Be |W] O}F [nel asi s|ci]ae) v Ge he) Sear Kr pNb|MolTe Rul rhe To [else [P| 'sb|Te| | [x ia Ro} FrBalac Lonthonides CoB AGE Pm BREUER EE TR Aetnides APO U Np Pu AmCmBK Ct Es FmMANo Uw Poses SELL dre, \\\\\, coment sncertain, (Xeitence uncertain, auion of the lterature with respeet t0 the existence and bonding of anhydrous nitrates, but no attempt was made to classify the covalent nitrates with respect 10 the mumbor of oxygens bonded to the metal atom. This topio, which is of areat structural interest, is discussed in the review by Addison and Logan {16a}. In some instances the twbe of hondine hax not clearly heen established. In others, which are discussed in this monograph, evidence forthe existence of the compound is shaky. ‘The alkali metal nitrates and the alkaline earth salts, except Be(NOs)s, are ioni, but otherwise there are no obvious criteria. For example AgNO; and Cd(NO.: fre lone, Dut GUND). and ZmlNUs) are covalent Co(NO3) exhibits characteristics of both ionie and eo: valent bonding The ionic nitrates generally melt to liquide which are stable to various degrees above their melting points. ‘These liquids can be distilled under reduced pressure {5A The covalent nitrates are eanerally not stable ne liquids. When heated, they first sublime, frequently giving stable molecular vapors, and then decompose. ‘The cation influences the decomposition through its ability 10 distort the nitrate ion. The decomposition enthalpies of the nitrates to N:Os and the metal oxide are linear functions of the cation property 182/2*, where 1'is the cationic radius and Z* the effective nuclear charge {109} A plot is shown in figure 3. trite of a given metal is generally much rate, the former can only appear as an unstable intermediate in the decomposition of the nitrate. This is particularly true for the covalent nitrates. x, both ealte may be more or less equally unstable over some tem- Perature range so that the decomposition reactions can become auite complex. This is particularly so since the salts may be oxidized or reduced by the gaseous decom Position products. For example, NOs produced by the decomposition of the nitrate may oxidize the nitrite also formed back to the nitrate. Since the experimental arrangement usually determines the gas phase composi- tion, reports by different authors frequently confit, In sueh eases the common features have been empha Tn the cate of the ionic nitrates, how 4 Phy. Chem Ref: Dota, Vo. 2, No.152 eat wees Ficute 3. Dependence of Ady ofthe nitrates onthe etion 7/2" or discetsion se text an 109 sized in this monograph. A consequence of the com- plexity of most nitrate decompositions is that the kinetic studies have usually been restricted to identifying the reactions. Even when rate constants and activation ‘energies are reported it is frequently not clear with ‘which particular reaction they are to be identified. 6. Decomposition Equilibria In view of the compleaities of nitrate decomposition the tabulation of system composition requires some ‘compromises. For example, although it is known that ‘over some temperature ranges alkali metal and alkaline earth mirates decompose to mitntes as a frst step, no high-temperature thermodynamic data forthe latter salts are available, Therefore the following procedure has been adopted: when good quality experimental decom: position studies are available these are discussed, The decomposition of the above-mentioned nitrates and a few others is treated in terms of decomposition to the oxide, e.g, for a divalent salt, M(NO;)»=MO+2NOs+1/2 Os a 4. Phys: Cham. Re. Dat, Vel. 1, No.3, 1972 KURT H. STERN and the gas equilibrium 2NO:=2NO +0, 2 ‘The reasons for neglecting other gaseous species have been discussed in the previous section. The approach is that used previously by Kelley [62a] and in all cases where nitrates are not stable represents the best approx- imation to the pl 1 The equ stants for reactions (1) and 2) are kjx PoP uta. PiaPos Prog Kam ‘The partial pressures of the three gases can be calcu lated if the nitrate and oxide do not form solutions (ayo= ano, =1) and if the only source of the gases is the salt. In addition to the equations for Ky and Kz @ ‘Hird relation is denved trom the tact that N and O must be liberated in a fixed atomic ratio, Thus Pop=W4(Pyg | Poo) 1 U2P 0 4Po= Prot 3Pyo- If the condensed phases are pure, a condition which can only hold if both the salt and the oxides are solids, the term ayolayosx=1 and appropriate substitutions yield an equation in Po, alone: KyE 3G.) Pat Pa 0 1g the su written in the form stitution X=PYs this equation can be where a=Ki"/4, B= (3/4)(KiK:)". This equation has only one real postive root for positive values of a and b but cannot be solved in closed form. Newton's method was used to solve it by steration. Aiter the solution for Po, had been obtained Pyo, and Pyo were ealeulated from the equations Prog = K/h Ys Pro (KK) "IPM ‘The pressures thus obtained are those to be expected if the pure nitrate is initially placed into a closed comDECOMPOSITION OF NITRATES AND NITRITES tainer containing no other reactants, and the system is allowed to reach euilibrium, Although the pressures in the real systems may differ from those ealeulated by the above procedure, par ticularly if nitrites are formed, the values obtained are ‘a uselul guide to the stability ofthe salts. In several instances the lack of high-temperature thermal data, particularly for the nitrates, prevented the caleulation of equilibrium constants at temperatures where it would be useful to have them. In these cases values of log K were obtained by log K versus UP plot. The temper been put in parentheses. K values calculated in this way are estimated to be uncertain by one order af magnitude Alternatively, estimation of K by extrapolation of Afef (uncertainty "3-2 Idee) would yield approximately the same uncertainty in K. For those salts for which no high-temperature thermal data are available a very crude estimate of K can be made from MG/T'=AH%q/P—ASix, It should be recognized, however, thatthe assumption of temperature invarianoe of AS* and AH® may roeult in large errors in K. All the partial pressures calculate librium constants assume a unit act condensed-phase components, This assumption is, quite good when these are solid. Above the melting point of the salts, however, continued decomposition of the salt will result in a solution containing dissolved oxide and the partial pressures will depend on the melt composition and will therefore change as the decompo- sition proceeds, Because of the form of Ki, the partial pressure calculation will be worst for melts containing ‘only small concentrations of oxide (@yo =0), but will bo correct when the salt ie approximately half decom- posed, from the equi ratio for the (ayo!ays004) = 1 ‘An examination ofthe various tables shows that O; and NO are the major products of nitrate decomposition, the concentration of NOs being rather minor. This results from the stoichiometry of the equilibrium 2NOs= 2NO+Os which lies to the right for low total pressures. Aluminum AI(NOs)s has been prepared in nearly pure form by vacuum sublimation of its adduct with NeOs. It con- densed as a white powder at ~78 °C. [6], None of its properties has yet been measured. Its classification as covalent is made on the basis of the spectrum of the IN:Os adduct, Barium BalNUeke ‘The meking point of Ba(NO.): is very much in doubt, Piekielay [25] giving, 96? °C, Prot Contnereewer a 759 senko and Bordyushkova [96] give 284 °C. Neither paper deseribes any experimental detail. Similarly, solid transitions were reported [97] at 203 and 230 °C, but no dotails are available. ‘The decomposition of the salt has been studied by three groups of workers [35, 84, 96] at somewhat dif- ferent temperatures and under various atmospheres. Although they differ in detail, they are in general agree- tment as to the main features, ‘The primary decomposition reaction, which is irre versible, is Ba(NO.}:=BaO-+NO,+NO, ® ‘This reaction begins as low as 250 °C. In the tempera: ture range in which Ba(NOs}: is stable the NOs formed oxidizes Ba(NO2): (118): Ba{NO:):+2NO:=Ba(NO:+2N0. — @) Above 400 °C, BaO reacts with NO to form Ne: BaQ+3NO=Ba(NOs)-+ 1/2Ns. 8 “Overall” reactions given by the various obtained from various combinations of react ‘The speed of the overall reaction and the distribution of products is evidently affected by the composition of the gas phase and the manner of its removal. For ex: ample, Protsentko and Bordyushkova [96] observed that in the range 410-440°C the rate varied in the order air > vacuum > argon. The rate in air may he greatest since 0 can oxidize NO which may increase the rate of 2). In argon the Arrhenius activation energy for a first order reaction 1s 05.3 KI. ‘The effect of gas composition and pressure on the temperature range over which the decompo: Alone oceur can be seen by compasing the abre with a TGA study under vacuum [92}, The first stage of the decomposition, corresponding to 2Ba(NO,),=Ba(NOsh+Ba0 +NO+1/2N: occurs between 90 and 150 °C. The second stage be- ginning at 450° and complete at 600°, is the decomposi- tion of the nitrate BalNOs):=BAV-+ZNUE+ 120s Ba(NO): Decomposition has been observed as low as 525 °C, but is still slow at 550° [85]. In fact, even the liquid salt decomnoses only slowly just above ite melting point (9, 5}. The frst stage of the reaction is formation of the nitrite RaNOe = Rae + Oe 4. Phy: Chem. Rel: Dea, Vek. 1, No. 3, 1972788 KURT H. STERN but this sal is very unstable so thatthe overall decom- Tensions Poston is — a¥0>n Ba(NOz): = BaO +2NOs + 1/20s. — tan | rom) | ad as |Reterenoe ‘As can be seen from she ealelated dimucintion _ dart) | amet ee) pressures in the table below, the dissociation might be = | cys ua txpected to be inhibited in air. This may account for 2 a % the stability obcorved by Addicon and Coldrey (9) ‘The salt appears to have no solid-state trans BoNOsie ot] ao [one | ome | oe Mat 123 K, from Alls: te mln pi anon ray | pecwy | Retrnees Theodyounic dats 29818 K) ae | am a so | sas 3 so | aur 3 Simo deg* | clmadog+ | Ret so | ae : ee ; aon an su » a | : Banoo. ia 8 ° | in i ho Te wea » oo | ae 3 au a uae I mol ‘keal mol! Ref. a8 58 aa Ba(NOs): 92.07 ~237.L Tb muon: cror | Tie | iy to cess | cis | Decompuiton of BNOne BuNO,= B40 +2N0, +12 0, tiny 904 EBA T | BaNOe| Bao | Afef | GT Pow Pao Pro Pr [PMOPN) tee [dees | face] tock | x a oa fe] os woes [a Be mas | -238|—v3 | ano | ws -cam | sana | rma0 | cian | sexio | ance foo | “m0 | “2a | a | ‘exe “san | 9'spei0-« Tapio | Saascios | anao-= sm | moma | mea |—auet | saa] canoe | tapcio-* Eopean-s | Laneio | Sanxo-* oo | “anes | to | “tana | dora| Savao | Soo | Lzexio> | 229.02 (ry sea | Teens | scm | thaws | aman | sixo «ico Zh5 | spans | ais” | sans | abo” | O36 ‘ato Tso | tomes | os | keane fom | tan 4. Pvt. Chom. Ref. Data, Vol 1, No. 8, 1972DECOMPOSITION OF NITRATES AND NITRITES 755 Beryllium Calcium Be(NOr)e Co(NOs): Be{NOz)e is a white, hygroscopic solid. The bonding between the metal and the nitrate group is covalent. On being heated abuve 125 °C it sayilly loses NOey with te formation of the oxide nitrate Be,O(NOs) [21] ‘Thermodynamic date (298.15 K) ‘aezen, aur Kimo! [_kealmo” [Ret BuNOn, waax8 | -w24en | 9 Bismuth ‘The proparation of Bi(NO,), has boon roportod Bond ing appears to be covalent [112] Cadmium Ca(NO.): ‘The pure anhydrous salt has apparently never been prepared, although it has been reported in reaction mixtures [59a} ca(NO,), ‘The infrared spectrum [11] indicates the salt to be a Lypically fonie solid, Since it decomposes rapidly above 573 K [65] the reported melting point is uncertain. The values of AH, and AS are obtained by extrapolati of cryoscopie data in AgNO, and TINO, [65]. The decomposition is reported to be reversible and to yield no intermediates [68] 2Cd (NO, =2CdO +4NO:+ 0 Taine 7m [ora [we 9] os | ae 88 1a, 65, esx) Toate [male Re canoe | ne A Sake 4 ee Than canon Gao ‘The solid-state transitions were obtained from heat: ine curves. The nature of the phases was not charac: terized [7], ‘The decomposition reactions of Ca(NO2) are similar to those for the Ba and Sr salts, Centnerszwer and Pickielny [85] measured the decomposition pressure over the temperature range 540-588 K. In an inert atmosphere log p is linear in 1/7. p varied from 0 at 540 K to 698 torr at 588 K. This suggests that a single reaction is responsible for the measured pressure, but it is not at all clear what this reaction is since the en- thalpy change caloulated by the authors from the pressure data (147.7kI, 35.3keal) differs considerably from AH%y for the reaction cited by the authors, Ca(NO}),=Ca0+NO+NO a for which AHisg=2344kJ. The lack of hich-tempera- ture thermodynamic data for Ca(NOz): prevents a com- parison of AH® at the temperature of the experiment. At somewhat higher temperatures only NO appears as the product, probably because NOs oxidizes the CalNOe CulNO.): +2NO:= CafNO3). +2NO, @ The decomposition was also studied by Protsenko and Bordyushikova [96] at somewhat higher temperatures, (693 and 723 K, which is still sufficiently low for the Ca{NOs): to be stable, or at least for its decomposition to bo nopligible compared te that of the nitrites They noted that the rate of decomposition varied with the sas phase in the order argon < air < vacuum. From an analysis of the gas phase and the weight loss of the sample they conclude that in argon the main reaction is the formation of the nitrate with partial reduction of the NO to Ni: 4Ca(NOs}e=2Ca(NO;),+2C80+2NO-+Nz GB) which is tairly consistent with reactions (1) and 2) above. From the firstorder rate constants they cal- culate an Arrhenius activation energy of 33.2k)(7.94 heal. Reactions (1) and (2) have also been found by Oza and Oza [87] who find that these reactions are reversible. ‘Thus, since the nitrate is unstable in the presence of NO, the production of N; is inhibited and reaction (3) will be minor unless the product gases are continually removed from the system, ‘The interpretation of the pressure measurements of Contnerszwer and Pickielny would therefore need to ee ae ee ceeeeeee bee eee een) le es count. In reaction schemes as complicated as the 4 Phys. Chem. Bef. Data Val. No. 1072156 KuRTM. STERN present one, equilibrium pressure measurements alone Tranions are likely to be of limited utility, particulary since the —<—- Partial pressures of the component gases depend not "eon | TUK) | alt et ‘only on the equilibrium constants of the reactions, but _| Se also on the composition of the condensed phase(s). CatNO es] 599 ” sat} as * calNO,), ssi] os 5 The salt exhibits no crystalline transitions. (55). Its — — decomposition has apparently not yet been studied in C¥NO%S—1] detail. Some indication of its stability may be gained from the thermodynamic data calculated forthe reaction Ca{NOs):=Ca0+2N0;+1/20s, Enthalpy and en: ‘Termodsnamie data 298.15 K) tropy increments listed by Kelley [3] were used in the = — calculation. Although the calculated dissociation pres sures are substantial above 700 K, it must be noted that ul Goldvey [9] fount ave liquid «0 be clear a z mot aee* |e 828 K and small bubbles to form at 833 K, but both of F . NO 13.3 162 these temperatures lie below the generally accepted CaNOvy Tent 33 » melting point of 84 K. The behavior of thie salt nearthe Ca 7 350 % melting point evidently needs more careful study. - — Density ce Wot? | keal mol 77 fe os canon, | —san0 | —ama8 | ay = — canon, | aa <1) » a 228 a 20 «50 | “ie | Decomposition of CxNOs CaNO;\= C0 +2N0;+ 1/201 Ln By A Kel T | canon) cao | ater | acir Po Pon Pro Pow pi dye [ete fase] me = ee He ee =202 |-1anas| moss | —naaer | ssosae | rorscex | sao] assim | sasio Tans |deres| ans | —as50 | 12sxi0% | Loncio | 2eexciom | sex in | 22710 soo | 2120 | 449 |—aaszr| sisan | 16.61 | aasxio-* | Lasxio+ | 202%10- 2a0x10-© oo | 2258 | 407 [soa | aa. | rome | a2oxio-» | 27axi0+ | 20010 6a5x10~ roo | “202s | —ce7 [nse | tooa2 | —s0 | zzexios | ranxioe | caomios | Leaxtoe | Sap « a | -2500| —se6 |-sso| 4577 | 230 | soxios |ozs | siexio7 | omg oa Cesium formation leads to some uncertainty in the enthalpy oy change. This problem is discussed in detail by Rao and Rao [100}, The new heat capacity measurements ‘Tho oale ie stable to 450 °C and deoompores to ths hy: mustajoki [3] permit calculation ot the tree-enersy oxide above that temperature if the product gases, NO and NOs, are removed (95]. In their presence the ni- trite is partially oxidized to the nitrate. cNO, This salt exhibits one solid oi transition. ‘The Iystereaie which ie frcpnent AA by thie trane- 4. Phy Cham, Ref, Dat, Vol. 1, No, 3, 1972 function of this salt up to 723 K, but the lack of Sigg and C, values for Css0 prevent carrying out thermody- ‘A serni-quantitative study [29] indicates that the salt Aecomposes only slowly up to 828 K, 0.05 percent ni- Fier heating for tom minitng trite eppesting in the wmDECOMPOSITION OF NITRATES AND NITRITES rex) | pteem) | References on 20M » on 235 * mo 226 » mi 205 » m2 2798 9 1 27m ” Cano, 2 368 st oo 2160 5 700 ands 5 20 27010 5 0 27608 5 0 2157 5 10 2M 5 787 may proceed through a series of oxide nitrates, but none of these is stable enough to give a plateau on TGA. ‘The first plateau is obtained at 200° and corresponds to CrOs. [7] Cobalt Co{NO:), ‘The existence of the salt has heen reported [38] but it must still be regarded as doubtful. It supposedly begins to evolve NO at ~ 100°C. CofNO:): Co(NOs} decomposes to CopOy in a single step with ‘ut formation of an intermediate [19]. The decomposition begins at 100-105 °C (19, 56}, but there is some question as to the temperature at which the decomposition rate fs @ maximum, Both (19] and (16) otato that tho + is @ maximum at 270 °C, but the experimental curve published by [19] shows this maximum approximately 100° lower. Thermodynamic date 298.15 K) 6206 1,605 10-97 mn | Ske exis] ee eee rs Prete ol Thermodynamic dita (298.15 K) Jmol deg-t feat molt dog-t | Ret ano, wer 8 + G0 ane Pr sit ~159 0 Chromium CHINO.) Anhydrous Cr(NOs)s has been prepared. The com- pound is covalent, When the pale green powder is heated in vacuum or an atmosphere of nitrogen it begins to decompose rapidly at 60°, and the decom- position rate 1s at a maximum at 100°, Decomposition calimat deg? | Ret % , Bes i, ae i Teale Ret 7005 rs soar | tb =a » Copper Cu(Non)e Reports about the existence of this salt are conflicting [58a]. Its preparation is doubtful Cu(NOJ. Below 500 heating of the sold salt results prtmnarly in the vaporization of the covalent molecule as a ‘monomer. In this temperature range the only thermal decomposition, into NOs + Os, is exhibited by the solid, ‘The "vapor if) more stable.” The vapor pressure of CuNOs)s was determined by Addison and Hathaway [12] by extrapolating pressure-time curves to zero time In order to subtract the pressures of NOs and Os, Their 0K) Poe) 02 032 60 050 4996 0a 1s W752 aan 1st 288 4988 359 A plot of log P versus 1/T is linear and yields a sub- limation enthalpy of 67.0 kJ. Above 500 K both the solid sud vapon phace salt dhcwupusr tv NOz | Or 4. Py. Chem. Re. Dat, Val. 1, No 31972158 KURT H. STERN Tralee Hafnium ro | an as [Re Although Addison and Logan [16] indicated the ws mot | Fmt deg existence of an anhydrous nitrate in their periodic coal table (fig. 2) there is some question whether such el Seeder as weno] 1 compound actually has been prepared. Field and Hardy — [45] succeeded in preparing the addition compound sey Hif(NO:)« - NsOs, but this compound sublimed as such, Themmaynamic dae 098.15 KY rather than losing NOs = Indium — carta Talaarmer | mar Theinfrared spectrum shows that In(NOs) is covalent des ott dee'' | Met and stable to at least 9° C since this was the tempera- cutvon. 1933 162 ‘4 ture ofits preparation [106]. 64.0 53.8 2226 » ea o ioe = ‘horrmamic data O98 16K) = any mot | keatmek —| Re aa In(NO) CutNO>s: 029 =14 RO) 108 cao “1a =i03 u coo =1st3 =306 % i - Wer tetea[ ha Gallium in(NOo, Teme | —isizeen | 93 Tmo. conig” | San » Ga(NOs)x was probably prepared in the anhydrous state by Dupié [49}, using vacuum delydraion of ee the hydrate at 40°C. A large fraction of the salt had decomposed to GasO; when the temperature reached 200°C. ‘Thermoynamic date 298.15 K) Famot-! deg-* | cal molt deg-* | Ret GaINOs a 208) 23 55.2. tb GaOulo) 84.98 m1 th up Md mal eal molt | Ret GaiNOs 09217 = Masten | 8 62048) 2. 68 » Gu0s'o) 1089 210.3 b Gold Au(NOs)s Evidence for the existence of this compound seems to he based solely on a report by Field and Hardy [5] who treated hydrated gold nitrate successively with HNO; and N:Os. Although the gold content corresponded to the trinitrate, no quantitative nitrate analysis was performed. Further information fo lacking: 4. Phys. Chem Ret: Dat, Vol 1, No.3, 1972 So far Fe(NO;} has only been prepared as the vol adduet Fe(NO,)*N.O,, although it is possible that Fe(NOs)s exists in the vapor state [13]. Lead PbINO), Very little is yet known about this salt. It has recently been prepared by treatment of the chloride with AgNU: ‘and its decomposition measured by TGA [92]. The de- ‘composition occurs in two stages, the first stage begin- ning at ~ 110° C being consistent with the stoichiometry SPD(NOz),= Pb(NOs}, + 2PbO-+ 4NO. ‘The second stage is the decomposition of the nitrate. However, this occurred in the range 320-450° C and seemed to proceed directly to PhO,r, results which are contradictory to other studies of nitrate decomposi tion (see below} PLINO,). Although there are as yet no high temperature thermo- dynamic data on Pb(NOs} available, the thermal ‘decomposition of the salt has been studied by a number of workers [23, 78, 120]. There is general agreement that decomposition occurs without oxidation of the Ph (fon to higher valence statoo, but itpEcompost: clear whether a nitrite may be an intermediate in the decomposition Bakeland [23] was the first to report a reversible decomposition of POs}: involving @ basic nitrate intermediate, but the most careful study seems to have been carried out by Neumann and Sonntag 78) who ‘measured the total pressure involved in three reversible equilibria and analyzed the solid phases. The equilibria (enotated fron the original paper) and dhe ranges over which they were measured are: TKK 1 539-682. 3Pb{NOs): =[Pb(NOs)e -2PbO]-+ 4NO;+0. TL 625-719 2{Pb(NOs): +2PbO}=[Pb(NO»): SPDO}+2NO;+1/2 Os TIL 688-809 [PD(NOs)»-SPbO]=6PbO +2NOs+ 12 Ox. ‘The overlapping of the temperature ranges is accounted for by the fact that the continued removal of product as ill result In the disappeanace uf 4 lowes uaide ‘and the formation of a higher one, with the resulting establishment of a new equilibrium. Nothing seems to be known as yet of the st of the oxinitrates so that the writing of the formula is somewhat arbitrary, e.g PD(NO,)s-2PDO=3PbO - N.Os. Neumann and Sonntag calculated equilibrium co stants for the above reactions by calculating the part pressures of NOs and Os, using the experimental data ‘of Bodenstein [27] for the equilibrium reaction NO;—NO+H/2 Op. Stace Usese difer but Hule fom those given in this monograph they were used to reanalyze the above three reactions. Tt was noted that a plot of In K of roact 1 UP could only very approximately be described as linear, but rather con: sisted of three linear portions. A plot of In K versus UT for reaction IIT could also more accurately be deseribed as consisting of two linear portions. For reaction II the plot was linear over the entire tempera ture range. AH? values calculated for the various portions ar Reacon | TVK) | ant) 1 59-585, om 583-03 oo 613-682 18 79 sr JON OF NITRATES AND NITRITES 750 lower two and may represent experimental error. The low-temperature plot of I shows more scatter than the plot atthe higher temperature. Using Hess’ law it is po the reaction le to calculate AH” for 6Pb(NO;)2=6PO-+12NO2+3 Os from the AHS for reactions 1, Hl, and IIL Using tor AH’, the average of the lower two temperature ranges fand the high-temperature range of III gives 1983k] for thie reaction. In the absence of high-temperature thermodynamic data for Pb(NOs}: a direct calculation for this reaction is not possible, but since AC is general- Ty relatively small, one would not expect AH" and AM to differ by more than 5 percent. In fact Ale = 1794KJ, so that the agreement is reasonable. A choice for AH, of 629k} would have lowered Affr to 1919K). IF it is assumed that AH” for each of three reactions is independent of temperature, AHJ* values ean be esti mated for the two oxynitrates. From AH’ = 629k] me get AU/* of [Pl(NOs) SPLO], AM y—924KI yields AH{* of [Pb(NO2):SPbO} The values are HPs) Pb(NOs)e-2PbO —867 Ph(NO;):“SPbO — 1558. When these values are used to calculate AH'y, 342k) is obtained, in good agreement with the experimental value of 337K). Recently a TGA study [92] of Ph(NOs): claimed the final product to be PbOs4, but no details were given. PUNO PbO (yellom) 70 a2 tb PDO (re) 5 69 ry aay PRINOws 4519 08.0 PbO (yellow) ate were ‘alelated from [3] and for’ MgO Yo dees [ead [Ret from [90]). Some of the difference may arise from the — dependence of the stability on the nature of the gas NNO me we B plse. Fer exsuple in a stonplere of NO, dec = posi has been observed as low as 400 K [86] At this temperature some Mg(NO:} was observed as product ‘This Inter salt derompaces st 280 K snd ean Moor [tetas | et therefore appear only san unstable intermediate in ——- the decomposition ofthe otrate. The liter i wnstable cme | om | inthe liquid state (21) The thermal decomposition of Despont MNO Mesoyn- M0280) 11201) 2255 19K F Manon ce ae | sci | wwe | | ry om | Pam | Paoatm | Pram soe: seen | Bee 400 | —1699 | —2049 | —s4ase| 193.37 | -10.101 | 79axi0-" | sasxio | Lirxie+ | s2axio+ | 156x104 sav | -ims [suse | sos) ‘outs | asm |zmane | lassie | danins | aapeins | eoncan | =o [ssn |-aom|—inm | ore] se [oan | 2m." | oan | Seo Mangane Reports as to the course of the decomposition differ somewhat. According to the older work of Guntz and ‘Marun 30) decomposition bewsns near 160° anu produces the dioxide: Mn(NO;}e=MnOs-+2NOs. More careful analysis of the remaining solid phase (42) shows that it is MnO; es and that both NUs and Us are evolved. Under dry No the decomposition rate reaches a maximum near 230°C (16). ‘The salt is characterized as covalent by Addison and Gatehouse [11], but Dehnicke and Strahle [42] find that it, like Co(NOs)s, possesses considerable ionic mat deg | camel deat | Ret MaNOsie 686 03 4 M0 son wan » Mao: 53.05 B68 » MiOs 05) 2a % MnO. 155.6 52 1% aur wmot | kealmo | Ret MatNOs 56.26 —as173, » sao 3.22 m0 » MnO sen 12429 % MnO 950.0 =z » Mas a isa08 391 » 4. Phys Chom, Re. Data, Vo. 1, No.3, 1972762 Mercury Hy(NO.). This salt appears to have been prepared for the first time by Ray [102] and in the pure state by Oza and Ezekiel (85). It is a yellow powder which begins to decompose at 50 °C and readily decomposes at 90°. HgO and Hg(NOs)z appear as products and so the reactions probably are 2Hg(NO2}e=2HeNOs +2NO_ Hg(NO;):=Hg0 +N.03, HgNO., ‘The salt has only recently been prepared [94] in the anhydrous state. It decomposes to a yellow solid with shave 100) the evalution af brown finmes when he °C. It appears to be covalent. Ha(NOs)s The anhydrous salt has heen prepared {11}, but le from infrared studies which indicate that the compound is covalent (11, 45] little has been done to determine its properties. The decomposition of the salt is appreciable at 160 °C and appears to lead to a basie nitrate, HgO-Hy(NO3)s- At 300 °C this compound is unstable and the nat product is HgO. In the presence of NO some nitri and NOs are formed (85). Thermod calmaltdea-t | Re Wao. ome Hatem | He0 (ed) 7029 1600 tb Wa samo? — | keal mol Ha(NO.» awsa7 | exten | 93 He0 (ed) co _| Nickel Ni(NO.). Ni(NO2): is stable up to 260 °C in an argon atmos- NNO, ‘The salt decomposes on heating, the initial decompo: sition, near 260°C, resulting in formation of the nitrite (06). 4 Phys. Chem. Ref. Dato, Vol: 1, No.3, 1972 KURT H. STERN ‘Thermodynamic data 298.15K) A Jimol-deg-* ] calmol"deg-t | Ret NaNO wo 9 + Ni(NOsk 1558 ates. 98 Nio 519) 9.08 wh ane Ky mel! ealmol? | Ret NuNOo 451 9.2, b NaNO cusei | -72¢en | tb No S07 =53 Palladium Paton: A compound of approximately this composition was reported to result from reaction of Pd(NO;): with NO as. PalNOs): Anhydrous Pd(NOs)s has been prepared (70), Its infrared spectrum indicates it to be covalent and it is sufficiently stable in the vapor to permit its sublimation in vacuum, ‘Thermodynamic data 298.15 K) fe SIrel des Ret PANO P40 ane wma! | teatime] Re Pann | aoe | onan | Pao. as K,.0-+NO,+NO. Between 410 and 460° the reaction sequence is (81, 89}: 2KNO, ~ K0-+ NOs +NO. a ‘The NO produced in (1) reacts with KNOs 2KNO:+2NO~ 2KNO5-+ Ne @ ‘The NO, produced in (1) reacts further K.0-+2NO, > KNOs-+KNOs 8 KNO,+NO,—> KNO,+NO. ® Which reactions are favored will depend largely on the atmospheric composition. For example, in an inert ‘atmosphere which removes the gaseous producws reaction (1) will predominate, Otherwise, since KNO, is stable in this temperature range and N; is unreactive, the mot reeult of reactions (1)-(8) is the production af KNOs and Nz. In an oxygen atmosphere, particularly in the temperature range 550-600° the reaction KNOz+ 1/20. KNOs goes to completion. In the range 650-750 °C KNO, becomes increasingly unstable and this reaction goes to equilibrium (see below) [25, 51, 108), Above 800 °C the reaction 2KNO,— K,O+ Ns-+3/20e goes to completion [51] KINO, ‘The phase transitions of KNO, are fairly complicated and have been discussed by several authors (76,80, 113]. In addition to the stable low-temperature orthorkom fort IK which eisfornie at 401 Kw tee slvwsboledsal I, there exists « metastable form IIT which can be obtained by cooling I to 396 K. III then transforms to If on further cooking at 386K, KNO, melts without decomposition to a liquid which is stable in air at Ieast to 530 °C [29]. When heated in air it hegins to decompose near 650° [51]. at somewhat lower temperatures at lower oxygen pressures. Between 550° and 750° the quasi-equilibrium KNO3 = KNO: + %O: is set up [25, 51, 108). The activation energy for the Forward reaction is 274k) (65.6keal mol"). Ik the Us 18 removed, KNO, decomposes, various oxides of nitroget are produced and the reaction is more complicated (see lscussion under KOs). KNO{0)=KNO.{l) + 40.19) tend to inter ‘As pointed out above, the to convert over a limited temperature range. Above the melting points this Ieads to solutions containing both salts. For some specified oxygen partial pressure. air, the solution composition is then a unique func: tion of temperature if equilibrium is established. In the range 550-750 °C the equilibrium has been studied by several authors [25,51, 108], 700 Freeman {51] studied forward and reverse reactions between 550° and 800 °C hy @ gas evalution method and found that equilibrium in one atmosphere O: was established hetween 650 and 750°. Sirotkin (108] meas- ured melt compositions in equilibrium with air over this temperature range, ‘The resulting discrepancy in AH® was studied by Bartholemew (25] in the light of his measured values, for Hr Hays for the sal, He conclu eat ve as rethod, in which the melt composition is caleulated from the volume of gas evolved by the decomposing KNO,, is more nearly in agreement with the thermo dynamic calculation. In this calculation it was assumed that the enthalpy increments for the salts could be extrapolated from the region in which they were meas- ured to the decomposition region. AH" caleulated from these thermal data agreed well with those based on the experimentally measured equilibrium constant. ‘The enthalpy merement for KNUs at (00 K agreed well with that listed by Kelley [3}. In the range 550-750 °C the equilibrium constant is given by the equation T1155 KJ mole 1025 J mole! deg 2.303 RT log K 2.303 R ‘The enthalpy increments given by Bartholemew can be used to ealeulate fef for both KNOy and KNOs. This calculation requires Siyy4, and AS for the phase changes. For KNOs these values are known and fef values at 700 K calculated from Bartholemew's and Kelley's [3] enthalpy increments agree quite well. The former's values have therefore been used to ealeulate fef for KNOs up to 1000 K. However. Six 45 for KNOs is somewhat uncertain and no thermodynamic data are svailatile for ition. Therefore, te expe mentally determined equilibrium constant for the KNO;—KNO; equilibrium is probably more reliable than 1 ealewlated val ‘sould he As esa, the partial pressures given for the reaction 2KNO, = Ke0-+2NO; + 1/20: assume unit activity for the condensed phases and the absence of other reactions. They can only provide a ough approximation to the actual behavior of a compl cated system. Density pleem)764 KURT H. STERN Density —Continsed “Teansions Pig em) = = oer Tanition [TaD] AW | as | Rae T | KNO. | KNOs | Ret 1d ol] J mol deg 700 anf 18056 | 5: KNO,....e—1 3 : te no [see ue | s KNO,..--|I (metasrbie. | a6 [230° [er | 76 m0 | em | 170 | 5 hobohedra) wo | ise | 178 | 5 Menthe wo | ism | ime | 5 shombieh no | vee | cre | s Kolemintetead | 396 | aor | z40 | 16 160 rt | =i m0 1m | 5 ust Jan} sae | ass | 700 ims | 5. To oor | 96 | ise | 200 im | 5 10 ims | 5 20 im | 5. 210 ums | 5 850) 19s | 5 Jmol! deg? | eat mot deat | Ref 60 uses | 5. ion “Toten | 3 a 1299) our = KNO, 162) x9 Sen K.0. on ns 10 as dol"! ealmol* | Ret ENO, 101690 118.220 in KNO,. 370.282 28.400 b K.0.. M82 = 6.8 no Decomposition of KNOx 2KNO,=K,0-4+2N0, +120, M9 =692.2, 165-4 kes] Poy Prox Pro Poa oak K am aim atm sn Lax 10-« Soe | Las x0 Feo.ans | Sap i0-™" | 2t6%c10-= | 820% 10-— TSiss0 | aio | L9%t0-x | 208 to-— Shien | EBB | sgoscaoes | Taio H31616 | 24x10 | SBI a0-H | 332% 10-" Saetst | Sabie | Sanco | 67x I0-" Sham | ss2xio= | Las%aos | 813% 10-% Sites | orm io | 255% 10 | 200% 10-* ar ape | 35x10" 15 15x10 | 29x10 roxio | 36x10 Radium ane Ra(NO:): Kd mot* ealmot! | Ref. According to Mellor [72s] the salt was first prepared Ra(NOs om a 1a by M. S. Curie, bur its properties seem not to have been Ra 508 us Ia studied since. Rare Earths Nitrites Jarier’ | eater | met Sayer anhydrous iin have evenly been pre RalNOoy a8 2 | Ta pared and their decomposition studied by TGA [92}. 0. ‘They all decompose at lower temperatures than. th 4. Phy. Chem Rel. Dota, Vol. 1, Ne. 8, 1972DECOMPOEITION OF NITRATES AND NITBITES corresponding nitrates. With the exception of prasco- ddymium nitrite whose decomposition product is PreOs. these nitrites decompose according to 48 (NO.),=2R.0,+12NO +30. Below are listed the initial decomposition and minimum oxide formation temperatures as given by 92). Intl decomposition temperature CC) Minimum oxide formation temperature C) NO. 20 a0 PANO 20 ‘0 NaNO 20 S10 SeiNO.)s 20 0 byte iy 00 0 YoiNOois ” “These authors also measured the decomposition kinetics of Nd, Dy, and Th nitrite. The reactions were first-order with very low (4-15 KJ) activation energies which they attributed to metal-oxygen interaction. Nitrates ‘There has recently been considerable discussion as tu fo) whether the anhydrous nitrates are ctahle inter. mediates in the thermal decomposition of the corre sponding hydrates and (b) whether some of the anhydrous nitrates are ionic or covalent. ‘A study of the infrared spectra by Walker and Ferraro [123] seems to have established rather firmly that the ‘anhydrous nitrates are covalent, Unfortunately, there appear to have been no TGA or other thermal decom positon studies of rare earth nitrates originally prepared in the anhydrous state, Both Wentland (124, 125) and Patil, Gosavi, and Rao [92] studied the thermal de- ‘composition of the hydrated salts. They agree that “oxynitrates of composition RONOs are formed as inter- mediates in nearly all eases, but differ as to whether the anhydrous nitrates are also intermediates. Wentland [125} found that the lighter rare earths—La, Pr, Nd— ‘gave the anhydrous salt as stable intermediate (R(NO5}- 6H 0 R(NOs >> RONOs > ReOs) whereas the heavier rare earths decomposed directly tw tlie vapwiteate, However, Patil ot al: [02] claimed thot ‘most rare earths on careful decomposition do give the ‘anhydrous nitrate as intermediate. However, they list dete thermal stability ranges only for thse sted below: ‘Stability ange of | Stability range of | Minimom exide miytowsmnene | RONG, CE) | termeinn co) temp. °C) LaNoy, | 210-20 515-515 10 NaOsn | 280-280 160-500 0 DyNony | 240-200 20-40 oo Yuin, | 240-270 0-800 00 LaiNO,), | 220-280 510-390 0 ms Pr(NOs)s is exceptional in that the final oxide is PriOvs. The hydrated cerium salt shows no stable mermediates, but goes to Ces ‘The above uncertainties could probably he cleared up by TGA studies of anhydrous nitrates. The above data indicate that these should be stable to ~ 300 °C. ‘The kinetics of the nitrate decompositions of Nd, Dy, and Yb were found to be first order with activation ‘energies ranging from 28 to 16 kJ higher than corre- sponding nitrites [92] Rubidium RENO; ‘The salt appears to be quite stable up to 450 °C and ‘decomposes mereasingly rapidly above that temperate [05]. The decomposition reactions appear to be similar to those of the other alkali metal nitrites, ie., the course of the decomposition depends on the exe phase TF the: ig is continually removed the reaction proceeds directly to the oxide: 2RbNO, = Rb,0+ NO-+NOs. In the pres tence of the nitrogen oxides the salt may be oxidized to the nitrate, particularly in the temperature range where the nitrate is stable. ENO, ‘The salt is stable up to 600 °C and begins to lose studied by Mustajoki [75], but the lack of a reliable entropy value for the salt and high-temperature data for lation of decomposition ea Jibria. Although no experimental studies of the decom: position seem to have been reported, itis expected to resemble that of the other alkali metal nitrates. Like the other alkali metal nitrates, the salt can be vacuum distilled above 350 °C. [58]. the oxide prevent the eal 71K) |ptzen) | References ENO, zn | ow 20 | 9 am | 9 am | 9 eae | eas | 9 220 |» 225 | 9 roxo, | am] ane | st so | 276 5 oo | 2466 5 om | Base 5 eo | 26 5 eo | aan 5 sw | 247 5 eso | 2a 5 eo | aor 5 om | 2398 5 oon | as 5 4. Phys Chem: Ref Date, Vl. 1, No.3, 1972786 kurt H. Density —Cominued TK) | eigen) | References mano, | 690 | 2378 s rm | 2369 5 io | 230 5 zw | 2389 8 mo | 2300 5 wm | 2310 5 p= 3.000.972 10- Transitions RDN, __ Transition Tm | al ‘as [Ret (ky mat] moltdeg*) 3a os | ax | in [a aos | 796 | Robidiom Thermodynamic data 98.16 KY alma dert [Ret BNO 106 586 ‘ BNO, : Rb. 24) 292) auf Wat [beam | Ref RLNOs(G, 1, 9.61 =n 6 RBNO. 3028 ~ a6 2 Rb. 380 79 ta Scandium Se(NOs)s Mollor [72] summarizes earlier work which claums preparation of this salt by heating Se(NOs) 41,0 in vacuum at 100°C. The melting point is said to ie the range 125-190", Silver AgNO: ‘The thermal decomposition of this salt has not yet been studied in detail, but preliminary experiments (92) indicate that it decomposes at 120° to give metalic, silver and NOs with first-order kinetics and an ac energy of ~29 KI. 4. Phy. Chem, Rel. ato, Vo, No.3, 1972 STERN AgNO; hein are complicated by ). This means that instead of the usual two simultaneous equilibria the system ean be considered in terms of the four reactions only three of which are independent: 2 AgNOs= Ag.0-+2 NOs +402 @ 2.NO.=2NO+0; ® 2 AgNOs=2 Ag+2 NO: +02 8 AgO=2 Agt+10., ® ‘Hquilbnum constants tor (), (3),and (8) have been listed. AgeO is quite unstable above 400 K and hence reactions (1) and (4) are not at equilibrium for reasonable pressues vf O2. Below 500 K, Py, is fixed by seaction (). Pyo, and Pyo can then be calculated from Ki, Ks, and Ky. Above 400 K the partial pressures were caleu- lated by a procedure analogous to that used for the other nitrates by assuming that only reactions 2) and (8) come to equilibrium, The partial pressures of the three gases calculated in this wav are listed in a separate table. Qualitatively, decomposition is negligible in the solid state, but hecomes appreciable 30-0° above the melting, point [34), ‘There has been considerable disagreement about the hheat capacity of AgNO. It was measured twice by Janz. and coworkers [61, 62] who used drop calorimetry to obtain data that differed considerably from those listed by Kelley [3]. Their work was criticized by Reins: borough and Wetmore [108] who pointed out that the sluggish transformation at 435 K may cause hysteresis. ‘They therefore employed adiabatic colorimetry and obtained agreement with Kelley's [3] compilation. The otter data were theacfine use iw this woke Data fon the reaction AgsO=2 Ag-+40s are taken from (111) Density ABNOs References x10DECOMPOSITION OF NITRATES AND NITRITES 707 Transtons MNO: = TK) | aH ay [Ret ad meth made C.ataerbombicd “6. ishombo- hed as | 2a 5s | 108 cpt aa | we | 20 | ‘Theempdynamie data (238.15 K) Jmol deg Ret ANU». 07 3.08) te MNO. 12820 Aco. m3 Ae 270 aur Wot | kealmalt | Reb AMINO 1439 20.18 % AINO. = 45.06, io ry Ae. 31.05 are th Decomposition of Ag. O ‘AOe)=2A4l+40xe) kJ. 47 KCal Aglet ‘tet | Reaction | ate sae | sort | mee | See! 29.15] —a2677 cass] arm Lox10 soo | 3.005 = 67.26] 9.863 |-0.313| 0.309 500 | 45.564 10.02} —7.929 }+0.813) 2.59 Decampostion of AdNOs (1) 2AgNOse)= AesOle+ 2NOsi) +404 AM, = 288.98 AJ, 67.86 CAD ARNO, Reaction r | te sci | tek | Jace! Jder eas |—14092| — e214 | sous | —27-707 oo [14st | 201 | 2am soo |-iss10] —sis87 | 1sa99 eo | S107 am | = Wy 2NENOKe)= ZAM ZUNE) UAE AM yg g=31497 WY, 75.28 KCl 0 495.0 | 300.68 | —15.708| 1.98%10 500 ~s2000 | va9.9e | 1982] 87x10 oo 165.71 | 59.2 | —3.098| 806% 10-+ Partial pressures at) forthe decomposition of ARNO: me] Pa Pros Pov Pr we iavxio-+ | Lasko Laps 10 ‘00 | 936x10-* | 4.78% 10-" 936x102 sto | 1.89%10-* | 2.79% 10 Sun% 102 ea0 | 791x102 | Loreto | 2%6x10-+ | 200x10+ oo | r72x10" | 786x104 | atex10+ | 196 Sodium NaNO; NaNO- is unstable above 330 °C [81]. The fist step in the decomposition is probably 2NaNO.—* Na:O +NO.-+NO. (N.Os is too unstable at and above this temperature to be significant.) Between 330° and 380° the reaction sequence seems tobe as follows: 2NaNO;=Na,0 +NO+NO;. ) ‘The NO produced in (1) reacts with NaNO NaNO; +2NO=2NaNO, +Ne @ ‘The NOs produced in (1) reacts further (118), NaO +2NO;=NaNO;+NaNOs 8 NaNO2-+NO,=NaNOs+NO. © Of these, at least reaction (4) is reversible 1161. Since NaNO; is stable in this temperature range and N; unreactive the net result of reactions (1)-(8) is the production of NaNO and Ns. If the gas phase is con- tinuously removed only (I) will occur. ‘At higher temperatures, 600-750 °C, NaNO; reacts with Os to establish the equilibrium with NaNOs: NaNOs=NaNO, +40s, 6 If the decomposition is carried out in an inert atmo phere the first decomposition product is Nz, accom- panied by increasing concentrations of Os in the later stages of the reaction [50]. The stoichiometry of this reaction can be written as [28] 2NaNO.—+ NazO-+Nz+ #0,, © Freeman (50] attributes the evolution of Ns to the formation of a superoxide which later decomposes to NazO aul Os. This view is alsv supported by Duel and Jacobs [28] who report that this reaction also proceeds in air. For reaction (6) the Arrhenius activation energy i civen by {501 as 187 KT (44.7 keal) and hy 28]as 169 kT (40.3 keal). For reaction (6) Ey=179 kd (42.8 keal (28) Both reactions are fitted by the equation [nay ]"9=ar 4. Pays. Chom. Re. Dot, Vol 1, No.3, 1972768 KURT H. STERN (a=fraction decomposed), an equation which was originally derived for solid state decompositions. Equations of this type generally desenbe sigmoid a versus ¢ curves. NaNO, NaNO; melts without decomposition to a liquid whieh is stable in air at least to 500 °C [29) and begins to de compose slowly at 600° {50}, Between 600 and 750° a pseudoequilibrium is established between air and a liquid containing NaNO and NaNO; whose composi is temperature dependent [50, 108), This equilibrium is discussed above. Enthalpy and entropy increments for NaNO; have been listed by Kelley [3] up to 700 K, but no such values are available for NaNOs. In the absence of suc data uy caleulation involving NaNOe cain be cartied out. In view of the complexity of the decomposi- tion reactions there is some question about the use- fulnose of euch caloulatione, As an example of the stability of NaNOs in the solid state, we are listing fragmentary calculations wl ‘can be made. These include a hypothetical decomposi- tion of NaNOs and an experimental study [108] of the equilibrium NaNO3(1)=NaNO(1) +40.(@). Since the Density Continued pigem) IK) | NaNO, | NaNO, [References om | um 5 ro | 1708 8 no | 1696 5 roo | eas 5 Tramiton | mK) | an | as | 1 molt |Jmat dee cor st |ro4zs] ass | ot NaNos cicr | se] 3% [ta | mts cr1 so |iss | a | ae ‘Thermodynamic da liquids are completely miscible and the solution virtually s ‘deal, the equilibrium constant K=PY(Xyaxou!Xnanos). Tome degt [eatmatider! | Re Density XaNy 163 ma a ateem) Rind, 1003 aa 2 Nao 7527 rm | no TUK) | NaNO, | NaNO. [ References 5 28 2200 B Gud Smo | eo | 1098 8. Wd mol! Kealmol+ | Ref. seo | um | im | 5 90 1.706 | 1.884 8 NaNOs 467.980 111.850 wb 600, ‘Lia | Ler 5 NaNO. 358.65 85.720, tb 10 um Le%0 5 Naso —415.9 99.4 10 eo | a | ime |S - _ oo | 176 | ass | 5 oo | 126 | tomy |S eo | in | an | 5 oo | uz | aan] 5 a | tome [awn | 3 oo | un | am | 5 Decompoion NANO, {0)2NaNOde)= Nake) +20) +400 fin 45862, 140. st T ] Neos | nwo | ane | sown Pe hm | ae Kf er | ear | sags | sat | tea = wm | am | am saert | sae eis | —ues1s | —z0 | ~sezs1| aswae [coon | aasaro~ | aazaio~| 199)» is in doubt since the determinations of it [35,96] vary by 37°. The solid phases have not been characterized, ‘The thermal decomposition has been studied by several authors (35, 88, 96) It is similar to those of the Darium and calcium salts, A measurable decomposition pressure has been reported at 264 °C, but most studies have been carried out at higher temperatures. At 400: 500°, where: Sr(NOs)s is stable, the overall reaction is sven as [96] 4Sr(NOz):=25xNOs): +2510 +2NO +N. From a careful analysis of all the condensed and vapor phase components in the range 540-700 °C, Oza and Patel [88] deduce the following reaction sequence: ‘SNOz)s # S1O-+NO-+NO:. o A part of the NOs reacts with the remaining nitrite Sx(NO:}e+2NO2—>SHNOs):+2N0. 2) In 0 closed eyotom this reaction may be reversible. The rest of the NO; reacts with the oxide, if oxygen is present S1+2N0,440,-+ SHNOs). a ‘The oxygen may be produced by the dissociation of NOs, NO: #NO+40s. ® Up to 600 °C reaction (8) produces nitrate while above ‘040 D1{IVUs}: decomposes. Nai produced by MNO): | 2NO. > Se(NOs)e | Ne ° Reaction (5) probably occurs only at the higher tempera- fires eines it wae nat reparted hy [28] holow 269 °C: Sq(NO,): ‘The melting point of S(NOq)2 is uncertain. The value listed is that selected by Lumsden [69], but Campbell and Gordon [55] report 891 K and Addison and Coldrey appear to be absent [55}. The ther Sr(NOs); has not yet been studied in any detail absence of high-temperature data prevent carrying out thermodynamic calculations. Its stability would be expected to lie between that of Ca(NOs): and Ba(NOs)s. Transitions ‘Sale rx) | at as Rel |) mat} molt des) sanion | ye [547 7 boa [556 a eo! [eeu 35,9 savov| et fois | a6 | sas “ ‘Thermedynamie dat 5 SxNO.y 1983 as ‘ SHNOS), 16, 2 ‘ Ret HNO»), » SaNO:), » ‘Very litle is known about this salt. Phase transitions have been reported but no details are given by the authors (97]. The thermodynamic data are estimates. mmo, ‘The heat of fusion of TINOs has been determined also by Kleppa and McCarthy [66] who obtained 9.47 kJ, but thear melting pot was 9° lower than the commonly accepted one. Rolla, Francosini and Riccardi 105} determined Hy Hayy valuce for solid and liquid TINO, which differ, particularly at the lower end of the temperature scale, from those given by Kelley (3). The vaporization of TINO. has heen studied recently hy Cubicciott [401 4. Phy. Cham Ref Dota, Vo. 1 Ne 9, 1972™ KURT H. STERN sn the range 539-613 K. He found that in addition to Densy NO as the decomposition product, TINO, also vaporized | — = TE as the salt, In the range 490-612 K the vapor pressure rien) of TINOs is given by logis platia)=—7486/T—10 loge TNO, a aa Ff T+21.77, and the enthalpy and entropy of vaporization % das 3 by Affyag U mol-?)=143,44—41.847, Say I deg" 0 er 3 mol-')= 370,996 og. He also calculated values of fef 510 ane 3 forthe salt and these have been used in this monograph = woods ‘The corresponding deta for TlO are those of Cubieciot oa eae 5 So im 5 560 485 5 Transtons —— as an [yaks ‘Thermodynamic Date 258.15) sak Transition | Kad lf deg | Re. TINO, few on = 1 69 m Tiotdeg* | alma dee-+ | Ret TINO, | Onborbombic>hexagana zat L0 [30 | te hhexagonal-seubic [416] 88 | 91 [59.04 TKOe roo at » Rimi fos] aa | ia |e’ TNO, irony Bete | m0 1% ” is any Ko | kealmats | Ret TINO, =m | —saa0 ry TNO. =sszis | 1s 10 a th Decomposition ef TNO, HIN0o= 11.06) +2NOd +100 Ain =STB SAL ad T | To, Ko] ter aor | tek | k Pa | Poo wo | Pe Jer! Ieee | wes | 107 m2 |—ss1s [aoe | 2anxio | aanxci0-™ sasxi0 ion are sas | —mose fovsio-# | 129% 10-"] s34300-" [asic 0-" 500 rite sno | is Tadeio- | rerio | Lebio- |asrxto eo | 13 aera | —1a9e8 | rosxao- | zorxio- | Lsixto- | 2670 | 48510 «00 64 ints | —s9er | torxae-m | tasxto- | exnctom | asrxio~ | La5xct0 Tin Zine sn(N0.). nih. Sn(NOs)+ melts at 364 K and begins to decompose at 371 K. No intermediate oxide-nitrate appears to form, ral product is SOs (27) Titanium TNO), Ti(NOs). is a covalent salt, stable at least to its melting point at 331 K [48]. It decomposes to TiO: with the evolution of O- and NO, 103]. 4 Phy. Chem Re. Dato, Vol 1, No.3, 1972 Zn(NOs)z is stable up to 373 K, and decomposes only slightly even at 513 K. Above this temperature de- composition becomes increasingly rapid, consistent with the equation [15] 2Zn(NOs)= 2Zn0 +4NOz + Oz. et :DECOMPOSITION OF NITRATES AND NITRITES m sup at | eet ar ZniNOre — 193.7 =us6 | 20. aM sao | tb Zirconium Hos) Anhydrous Zr(NOs)y has been prepared. It can be purified by sublimation. ‘The compound is covalent and very hygroscopic [46]. Acknowledgements Lam greatly indebted to Miss Brenda Gibson of the International Telecomputer Network and Mr. Curtis T. Ewing of the Naval Research Laboratory for working oat approptiate computer progiams for the solution of the equations in section 6. References Goneral ‘oe lollowing reerences 1m ths bibography Rave proved tbe enerally weful in the preparation ofthis paper and were used 20 frequently that no specie page numbers are Ben: {is} Rossin, F.D., Waganan DD. Evans, W. H, Levine, Sand “fe, L, "Selected Values of Chemical "Thermodynamic Properties”, NBS Cine 500, 1952 [ub] Wagmean, D.'D., Evans, W. HL, Halow, Ty Parker, V. Ba Balley, S. Mand Schumm, R. HL, "Selocted Values of Chemical Thermodynamic Properties", NES Tech. Noto 270-$(196, 270-1969, [nb] isthe ongoing revision of [La Values for "and S* 296.15 K forall salts and oxides inthe present monograph te taken fron [Ib whenever available. Ta some nrtance ‘ata nt yet published by the authors axe alo included, [2] Dow Chemical Company, ‘Thermal Laboratory, “JANAF ‘Thermochemical Tables”. (US. Dept. Commerce. National ‘Tecnial Information Service, PB 168-870) 1968. (b)Farst Addendum (1 168-370-1) 1966. {6)Second Addendum (PB 168-870-2196. "Pe completion wae weed for al the thermadymamie eo ction of nitrogen, oxygen, ad thee compounds {3} Kelley, K. Ke "Contitions to the data on theoretical metal Targy XIUL High temperature heatcontent, heat capacity, US. BuMines Bull 58,282 p. (1960, Unless specially referenced in the text all fee eneray fanetins listed in this monograph were caeulated fom values Ofte ann Se Sone Hy {) Latimer, W. M, "The Oxidation State of the Elements and “Their Potentials in Aqueous Solutions", 2nd Pa. (Prentice Hall, N.Y. 1952) 4m several mstances enthalpies and entropies at 298.15 timated by this athor ave Hated when no measured values ‘were avaiable [5] Jans, GJ, Dampier, F.W., Laksbminarayanan, GR. Lorena, .K., and Tomkins, RP, “Mlten Sale: Volume 1 Eee twical Conductance, Density, and Viscosity Data", NSRDS- NBS 15,1968. All density values of maken nitrates and nities which were ated in this monograph have been transcribed fate the present wark Specific References {6} Addison, €.C., Boorman, P. M., and Logen,N, J. Chem. Soe [7] Addison, C. Cand Chapman, D.J.1.Chem- Soe. 540(1968. [6] Addison, CC, and Chapman, D.J-J. Chem. Se. 589196. [9] Adon, Cand Coley: J. M.,J. Chem. Soe 468 1961 luv} Adasen, C. C, Garner, c.., Simpson, W. ., SuON, Pan ‘Wallwork, S-C.,Proc. Chem, Soe. 367 2968, [00] Addison,C.C, and Gatehouse, B. Ml, J-Chem.Spe618 (1960, {12} Addison, C.C., and Hathayay,B. J.J. Chem. Soe 3991958, US) Adivon, C. C, Hathaway, J. and Logan, NJ. Chem, Soe 10858) {8} Alison, CC. Johnson B.F-6., Logan, NE. and Wojcik, A Proc. Chom, Soe 3061961. 105) Addison, CC, Lewis, J, and Thompson, RJ. Chem. Soe. 229 (1951). {61 Addison, C. Cand Logan, N., Adv. in Inorg, Chem, ard Radiocher, 6,72-142(1968), (a6e) Addison, C.-C and Logan, 8. Preparative Inorg, Reactions 1, 141-168(1960, [27] Addison, C.C., and Simpson. W. B,J. Chem, Soe. $98 1965) Tig] Addison CC. and Sutton. D. Tonge. Chem. 2.228 (968, [09] Addison, CC. and Suton, D. J. Chem, Soc. Suppl No.1 3588 1964 [20] Addison, ._C., and_ Suton, D., “Progress in Inorganic Chemist", VoL 8, F. AL Coton, ed dntercienee, NY. 17 pp. 195-206, [21] Addison. C. C., and Walker. A. J. Chem, Soe. 1220 (968) [22] Andeeva, T. A. and Poosenko,P. 1, law. Vysehikh Uchelam “Zavendeni Khim. Khim, Tekh. 4.892 0960, [23] Boekeland LJ. Am. Chem Soe. 26,381 1904) [24] Bagnall K. W., Robertson, D.S., and Stewart, MA. J. Chem Sec. 888 0958. (251 Renney. RLF. 5. Phys, Chem. 70, 34421960) [26] Backs. J. O'M., and Richards, NE, Proc. Ry. Soe. A241, ‘W950, [27] Bodenstein. M,Z. Phy. Chem. 100, 6811922, [ral Bond’ BT sendJoncbe-® W Mod Chom Sem A. 196586), [25] Bordyushhova. BA, Protenko, P-L, and Venerovekays. LN, 1 Appl Chem, USSR 40, 1586 (1967, [30] Bridgman, P. W., Proc. Am. Acad, Art and Sei. $1,608 (915) [1] Dereon) Ann. Chim By 1 0927), [82] Cenonersewer, MJ. Chit. Phys. 27,9 (0980) [33] Genmerswer, ML and Blumenthal. Bull. tern, Acad Poon Sei. Ser A, 470(196). [24 Comncrarvers My end Dlamcothal Mc, Dal, Hotein, Acad Polon. Sc, Sex A 42.1930. [35] Centersrver. ML, and Pickilny, W., Bull Acad. Pol 9A, 38941955, {30} than, Ds yen ew Oy “Apo teoecopy tothe Analysis af Inorganic Ni Test Rpt. T-69-3-1, Dept. of the Army, Frankford Arsenal, March 1969. {o4 nea, 7, and Jonson, #4. Fnys Cem. 08, 2299 302) [38] Chrétien, A., and Long. ¥.. Compt, Rend. 217, 508 (198) {59} Gottn,F. A’, end Wikinon, C., “Advanced Toorganie Chem istry" 2nd ep. 39 Uaterecience. N.Y. 1966 90) Cunicen Dg Lemp 62,151 (970 {it} Cubicciat, D. end Eding HJ. Chem. Eng: Data 12,548 1967, [22] Dehnicke. K. and Strtble. I. Chem. Ber. 97, 2502 (960) [49] Dupe, A Compt. Rend. 86, 720(187 (48) Erdey {Liptay Cand Gil, Tanta 128881509 115] Field B.O.,and Hardy, C.J Chem, Soe, $828,196 [a6] Field. B.O.,and Hardy. C1, Proe: Chem. Se. 161962) [a7] Ped, B.O.,and Hardy, C.J... Chem, Soc. $28 1968). 4. Phys. Chem Ref. Date, Vol. 1, No 3, 1972™ KURT H. STERN [48] Field, BO. and Hardy. C.J. J-Cheém Soe, 5278 195), [a8] Feld BO. and Hardy, C.J,Qaaet- Rev. 18,361 (1968, [29] Francosin ., and Sinise, C, Ricerca Sc Rei) A3.411 (1963) [30] Freeman. S.J. Phys: Cher, 60,1387 1956) [51] Froeman.E.S.J. Ar. Chem Soe 79,888 1957. [52] Freeman, FS. and Anderson.D. A. Netare 199,68 (1960). [S31 Gatehouse, BM, J. Ire, Nucl Chem 8, 79 1958). (53s) Ginelis's “Handbuch ‘der Anorganischen Chemie Sih ed. ‘Verlag Chemie bl, Weinheim. Germany. (581 Goodwins HM. and Kalmus, H.T., Phys Rev. 28,1 (190) 15S] Gordon, .,and Campbell,C, Anal Chem, 27,102 1985). [56] Gunter A. and Martin, M, Ball. Soc, Chim, France 7,315 1910, [57] Haigh F. LJ. Am. Chem Soe. 34, 1137(1912). [58] Hardy, C1. and Field. B.0.,J. Chom Soc. 5130 1963), (591 Hovi, V. Aroll, Ac. and Vartova, M. Ann. Acad. Se. Fean, AVE, No. 39 1959 60] Halsmana, 0. and Bits. W., Z_ Anorg Chem. 219, 357 1930. (61) Jane, G. 1. James, D. W., and Goodkin, J.J. Phys. Chem. 68, {62} Janz, 6. J, and Kelly. K.J. Phys. Chem. 67, 2848196) [02a) Kee. K.K., US. Bur Mins, Rpt of Investization 3276 (1944. (63) Ketelaa.J. AZ. Keyat 98,388 1936) (6a) Hloppo:OvJnks Phyo Chem Coie, 89,019 9605 [65] Kleppa. 0.1. and Meschel,S. VJ: Phys, Chem 67,902 (1963 [G6] Kleppa. O. J, and McCarthy, F. J. Chem, Eng, Data 8, 531 (1963) (62) Keadomohio 114,957 1967), (68] Krause. H., Apparatehau 42,265 (1950) [6] Lumsden, J, “Thermodynamics of Molen Salt Miatures™ {caeaie Press ¥. 190 [70] Manehot. W., and Waldmuller.A., Ber. Deut. Chem. Ges. 59B, 2545,1026) (71) Markowitz, M. M.. Rice. J. E., and Winterita, P,P. J- Amt ‘Chem, Soc. 77,3382 1950). [72] Mellor. J. W.. "Comprehensive Treats’ on Inorganic Chem intry”, Vo V, p93 Longmans Green, NY., 1924. [724] Mellor, J. W., “Comprehensive Treatise on Inorganic Chem fatty Vol IV, pls Langman Greon. NT 192) [73] Mustajoki, A. Saom, Tiedoskst Toim. Ann. Acad Sei. Fenn, ANE, No. 5195) (74) Mantgjok. A, Suom. Tiedeakat Teim. Aan. Acad. Soi Fenn. ANE, No. 7495). (75) Muntgoki. A, Suom. Tiedeakat- Toim. Aan. Acad. Sci Fean, AVI, No. 91958). (76) Mostjo. A. Ann, Acad, Sci. Fenn. AVI, 99 (1966) [27] Neumann, Band Sontag, ZZ: Elektrochem, 88, 94 (1582. [78) Neumana. B., and Sonatas, AZ. Elektzochem. 89, 9 (1933 {79] Neumann, B., and Sonntag. AZ. Elekrochem. 41,611 (1935. 180] News D. M.-and Staveley. LA. K..Chem, Rev. 66.267 (1956, [81] Ora. J-M. Jc indian Chem, Sc. 22,178 (1945. [22] Ora. Mand Dipl. NL, J. dian Chem. Soe. 27, 305 10950), (82) Oe TOM aed Bone 1 Sef te Ree 91R, 56 1069) Tet} Ora. TM, and Jha. JC. J Indian Chem, Soc. 48, 79 (196, [a5] Ora, TM. Tha, JC, and Exekiel,E.1,J- Indian Chem. Soe 45,4201. (86) Ora. TM. and Mires BV. Indian J Chem 3, 200 (1965, (87) Oza, 7. M, and Oza, 0.1. Chem Soe. 97 (1958, [e3) Ona, T. MC and Patel §.A.,J Indian Chem, Soe, 81,519 1954). [29] Ora. T., and Walawalkar.B.R. J. Indian Chem. See. 22,243, 0986) 4 Py. Chem. Ret: Data, Vl. 1, No wn [pu Park [2] Pat K. C2 Gonav, KK and io, U- NK. Inorg Chi. Acta 1, 185 1967, [93] Plekoukin. V. KJ. Appl Chem, USSR 40, 2470 1967, (04) Pots. R.A and Aired. A. Le, Inorg. Chem. 5, 1065 1966. [95] Protenko, PL and Bordyashkovs, EA Russ. J- Inorg. Chem, 10, 657 0865) [96] Protscako.P.L. and Bordyushhova, EA, Russ. Phys. Chem. 39, 1089 1965). (07) Protenko, P-L, and Brykova, N-A., Rusa. J Inorg Chem. 8, 1130 1963), [28] Prtsenko, P. L, Prtsenko, A. V. and Ravumouskaya, 0. Ns, ase J Tore, Chem. 10, 45 (1965, [99] Prottenko,P- sand Protenko, A. V.-RussJ. Phys Chem. 38, 1460 1968), (200) Rao, KJ. and Reo. C.N. R., J. Materials Sei, 1, 238 1965, [001] Ran KT” and Raw NR “Pragroes in Sali State Chem Jnty." Val 4.1. Reiss, ed. (Pergamon Press, NX., 1957) p 1. [002] Ray. P. C2, 1. Chem. Soe 523 0908) [B02] Raton, HL and Hales A. Lich. Ann 452,47 002, [008] Reinsborovgh, V. C. and Wetmore, FE. W., Australian J. Chem, 20, 1 967, (105) Rolla, M., Francosin .. and Riceardi,K, Discusion Faraday {006} Schmeiser, ML, and Kabler 6. Angew. Chem. 77,496 (1965, [007] Shomate, C.1L,4- Am, Chem. See. 66, 928 194, [D08) Sizotkia, ©. D., Russ. J. Inore Chem. 4, 1180 195%. (009) Sten MJ Chen. Rue 46, 64 (190 [010] Ste, KH. and Weise, EL, “High Temperature Propestion ‘nd Decomposition of inorganic Sas. Par 1, Salfates.” Nat Stand. Ret. Data Ser. NBS (US). 7 (1966) (011) Stem, KH. ad Wel. . Ligh Tenperacae Propetion ‘nd Decomposition of Inorganic Sele. Part 2. Carbouates.” Nat, Stand. Ret. Data Ser NBS (US, 30 1960, (029] Staub, D-K, Siler, H.H., and Ryschkowitech,G.., J. Inorg, ‘Nal Chem. 24,919 (S82 {213} Suomme, K-O,, Acta Chem. Seand 23, 1625 (1969) [114] Steomme. KO. Acta Chem. Seand. 23, 1616 0969) [115] Strsmme, K.0. Acta Chem. Seand 28, 16251969). [016] Saper J. and Fisxman, KZ Anore. Chem. 206, 257 (1952 [DIT] Thomas, M.U., Bull Acad. Sei. 1698 1908 [118] Vestn. FJ. Appl Spectey. 18, 59 (1959, 1119] Veatny. F and Cugoua. FJ. Inorg. Nucl Chem. 20, 252 ‘1900. [120] Vrain. F. and Gugiowa, FJ ore. Nucl Chem. 28, 1129 (0963). Iu2il Vrotne. F. and Honig, J. M., Trans. Faraday Soe. $6, 1051 (1960), [222] Wait,S. Cand Janz, C.J, Quart, Rv, 175 225 (196 [i25] Walker, A. snd Ferraro, J. RJ. Chem. Phi. 48, 2689 (1965), [094] Wendlands W-W., Anal Chim. Acta 1S. 488 (1956 [u25] Wendland, W. W., and Bear. JL, J. Nucl Chem. 12,276 (0960), (226) Witeos.D-E.,and Bromley. L_ A. Ind. Eng. Chem. 85,32(1963), (097) Wolf Pad King, M7. Kee RT, 79103) (128) Ziegler GE, Phys. Rev. 38, 1080 1981) [129] Ziegler, 6. . 2 Krys. 94, 491 1986).