Pressure of dissociation

Halides and Oxyhalides. Thermodynamic data have been presented for MF compounds (M = Nb or Ta, n = 1—5). ° The equilibrium pressure of dissociation of NbBr4 into the penta- and tri-bromides, as... 

The assumption that the partial surface pressure due to the single molecules is constant throughout the transition is equivalent to saying that the micelles have a constant surface-vapour pressure of dissociation Fj. The manner in which this varies with temperature is most interesting. Langmuir found that the difference Fj—F0 obeys an equation of the Clapeyron type ... 

FIGURE 1.13 1 Low boundary of the oxygen-ionic conductivity for the solid (Zr02)o.9(Y203)o 1 electrolyte and 2 and the temperature dependence of logarithm pressure of dissociation for oxide Na20. (From Zhuiykov, S., Electron model of solid oxygen-ionic electrolytes used in gas sensors, Int. J. Applied Ceramic Techn. 3 (2006) 401-411. With permission.)... 

In each case, therefore, there are three phases present, two solid phases and one gas phase. The systems are, therefore, univariant and to each temperature there must correspond a definite pressure of dissociation, quite irrespective of the amounts of the phases present. The values of these dissociation pressures are given in the following tables — ... 

As in the case of sodium sulphate, the transition points of the different hydrates would be indicated by breaks in the curve of pressures. Finally, mention may again be made of the difference of the pressure of dissociation of the hexahydrate according as it becomes dehydrated to the a- or the jS-tetrahydrate (p. 186). 

The flow can be radial, that is, in or out through a hole in the center of one of the plates [75] the relationship between E and f (Eq. V-46) is independent of geometry. As an example, a streaming potential of 8 mV was measured for 2-cm-radius mica disks (one with a 3-mm exit hole) under an applied pressure of 20 cm H2 on QT M KCl at 21°C [75]. The i potentials of mica measured from the streaming potential correspond well to those obtained from force balance measurements (see Section V-6 and Chapter VI) for some univalent electrolytes however, important discrepancies arise for some monovalent and all multivalent ions. The streaming potential results generally support a single-site dissociation model for mica with Oo, Uff, and at defined by the surface site equilibrium [76]. 

By introducing a collision gas into Q2, collision-induced dissociation (CID) can be used to cause more ions to fragment (Figure 33.4). For example, with a pressure of argon in Q2, normal ions (mj ) collide with gas molecules and dissociate to give mj ions. CID increases the yield of fragments compared with natural formation of metastable ions without induced decomposition. 

Reaction 1 is highly exothermic. The heat of reaction at 25°C and 101.3 kPa (1 atm) is ia the range of 159 kj/mol (38 kcal/mol) of soHd carbamate (9). The excess heat must be removed from the reaction. The rate and the equilibrium of reaction 1 depend gready upon pressure and temperature, because large volume changes take place. This reaction may only occur at a pressure that is below the pressure of ammonium carbamate at which dissociation begias or, conversely, the operating pressure of the reactor must be maintained above the vapor pressure of ammonium carbamate. Reaction 2 is endothermic by ca 31.4 kJ / mol (7.5 kcal/mol) of urea formed. It takes place mainly ia the Hquid phase the rate ia the soHd phase is much slower with minor variations ia volume. 

The dissociation pressure of pure carbamate has been iavestigated extensively (10—12) and the average values are shown ia Table 5. 

Table 5. Vapor Pressure of Pure Ammonium Carbamate at which Dissociation Begins...

Ammonium bicarbonate, also known as ammonium hydrogen carbonate or ammonium acid carbonate, is easily formed. However, it decomposes below its melting point, dissociating into ammonia, carbon dioxide, and water. If this process is carefully controlled, these compounds condense to reform ammonium bicarbonate. The vapor pressures of dry ammonium bicarbonate are shown below (7). (To convert kPa to mm Hg, multiply by 7.5.)... 

AH ammonium haUdes exhibit high vapor pressures at elevated temperatures, and thus, sublime readily. The vapor formed on sublimation consists not of discrete ammonium haUde molecules, but is composed primarily of equal volumes of ammonia and hydrogen haUde. The vapor densities are essentiaHy half that expected for the vaporous ammonium haUdes. Vapor pressures at various temperatures are given in Table 2 (11). Latent heats of sublimation, assuming complete dissociation of vapors and including heats of dissociation are 165.7, 184.1, and 176.6 kJ /mol (39.6, 44.0, and 42.2... 

Reactant. Steam can behave as an oxidant. The partial pressure of oxygen generated by the dissociation of steam into hydrogen and oxygen is shown in Figure 17. 

These data can be used to obtain the value of the equilibrium constant at any temperature and this in turn can be used to calculate the degree of dissociation through the equation for the conceiiuation dependence of the constant on the two species for a single element, die monomer and the dimer, which coexist. Considering one mole of the diatomic species which dissociates to produce 2x moles of the monatomic gas, leaving (1 — jc) moles of the diatomic gas and producing a resultant total number of moles of (1 +jc) at a total pressure of P atmos, the equation for the equilibrium constant in terms of these conceiiU ations is... 

In the case of hydrogen, for example, at a teiuperamre of 2500 K, the equilibrium constant for dissociation has the value, calculated from the tlrermo-dynamic relation between the Gibbs energy of formation and the equilibrium constant of 6.356 x 10 " and hence at a total pressure of 10 atmos, the degree of dissociation is 0.126 at 2500 K, which drops to 8.32 x 10 at 2000 K. 

It can be readily calculated that pyrite will exert a sulphur dissociation pressure of 1 atmos only at 1512K. However, when the sulphide reacts with air the main gaseous product is SO2, and the reaction is then... 

The sulphur dissociation pressure of Fe/FeS at the matte blowing temperature of about 1573 K can be calculated from the following data... 

For example, in the case of dilute solutions, the van t Hoff s equation may be used to piedict the osmotic pressure (jr = CRT) where n is the osmotic pressure of the solution, C is the molar concentration of the solute, ft is the universal gas constant and T is the absolute temperature, Fm dissociating solutes, the concentration is that of the total ions. For example, NaCI dissociates in water into two ions Na" " and Cl . Therefore, the total molar concentration of ions is hvice the molar concentration of NaCI. A useful rule of thumb for predicting osmotic pressure of aqueous solutions is 0,01 psi/ppm of solute (Weber, 1972). 

The species H2 and H3+ are important as model systems for chemical bonding theory. The hydrogen molecule ion H2+ comprises 2 protons and 1 electron and is extremely unstable even in a low-pressure gas discharge system the energy of dissociation and the intemuclear distance (with the corresponding values for H2 in parentheses) are ... 

Figure 8.19 F.llingham diagram for the free energy of formation of metallic oxides. (After F. D. Richardson and J. H. F. Jeffes, J. Iron Steel Inst. 160, 261 (1948).) The oxygen dissociation pressure of a given M - MO system at a given temperature is obtained by joining on the lop left hand to the appropriate point on the M-MO frec-energy line, and extrapolating to the scale on the right hand ordinate for POi (atm).

BrNO dissociates reversibly into NO and Br, the extent of dissociation being 7% at room temperature and 1 atm pressure. A similar reversible dissociation occurs with CINO at higher temperatures. 

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