526. Studies of gradual transitions in mixed crystals. Part I. The system ammonium chloride–ammonium bromide

1950 ◽  
Vol 0 (0) ◽  
pp. 2736-2743 ◽  
Author(s):  
C. J. Mandleberg ◽  
L. A. K. Staveley
Keyword(s):  
Ammonium Chloride ◽  
Mixed Crystals ◽  
Ammonium Bromide

The thermodynamics of mixed crystals of ammonium chloride and ammonium bromide. - III. The heat capacity from 8 to 300 K of solid solutions of composition NH 4 Br 0.20 Cl 0.80 and NH 4 Br 0.74 Cl 0.26

1981 ◽  
Vol 375 (1762) ◽  
pp. 351-359
Keyword(s):  
Heat Capacity ◽  
Ammonium Chloride ◽  
Solid Solutions ◽  
Mixed Crystal ◽  
Mixed Crystals ◽  
Ammonium Bromide ◽  
Ammonium Ions ◽  
Β Phase ◽  
Δ Phase ◽  
Entropy Of Transition

The heat capacity of the mixed crystals NH 4 Br 0.20 CI 0.80 and NH 4 Br 0.74 CI 0.26 has been measured from ca . 8 to 300 K. The first of these solids has, as expected, two gradual transitions, the lower having an entropy of transition ∆ S λ of 3.79 J K –1 mol –1 , and the upper a ∆ S λ of 4.51 J K –1 mol –1 . The heat capacity between these two transitions is always considerably above the ‘normal’ or baseline value, and it appears that the orientational disordering of the ammonium ions, while completed in the γ → β transition, commences in the δ-phase. The other, bromide-rich mixed crystal shows no sign of a δ → γ transition, but has a λ -type γ → β transition which culminates at 262.5 K, with ∆ S λ = 7.31 J K –1 mol –1 . The heat capacity of both mixed crystals in the β-phase, like that of the pure components, is ‘anomalously’ high, the additional heat capacity for the solid solutions being larger than that for the pure salts. The phase diagram for the ammonium-chloride–ammonium-bromide system is shown; it combines previous information with that provided by the heat-capacity results reported in this and previous papers.

The thermodynamics of mixed crystals of ammonium chloride and ammonium bromide. I. The heat capacity from 8 K to 476 K of an approximately equimolar mixture

1980 ◽  
Vol 372 (1751) ◽  
pp. 489-496 ◽  
Keyword(s):  
Heat Capacity ◽  
Low Temperature ◽  
Thermodynamic Parameters ◽  
Ammonium Chloride ◽  
Mixed Crystal ◽  
Mixed Crystals ◽  
Equimolar Mixture ◽  
Ammonium Bromide ◽  
Cubic Crystal ◽  
Type Transition

The heat capacity of a mixed crystal of ammonium chloride and ammonium bromide, of formula NH 4 Br, 0.55 Cl 0.45 , has been measured for temperatures in the range 8-300 K in one calorimeter, and 270K-476K in a second calorimeter. The mixed crystal undergoes a >.-type transition at T = 271.2K, and an essentially isothermal transition, to a facecentred cubic crystal, at 382.8 K. At this second transition, considerable superheating of the low-temperature form and supercooling of the hightemperature form can occur. Thermodynamic parameters for the mixed crystal are given at rounded temperatures.

The thermodynamics of mixed crystals of ammonium chloride and ammonium bromide. II. An analysis of the heat capacity of ammonium chloride, ammonium bromide, and an approximately equimolar solid solution of these salts

1980 ◽  
Vol 372 (1751) ◽  
pp. 497-516 ◽  
Keyword(s):  
Heat Capacity ◽  
Ammonium Chloride ◽  
Mixed Crystal ◽  
Spectroscopic Properties ◽  
Ammonium Ion ◽  
Ammonium Bromide ◽  
Lattice Vibrations ◽  
Ammonium Ions ◽  
Torsional Oscillations ◽  
Β Phase

The heat capacity C p of ammonium chloride, ammonium bromide and the mixed crystal NH 4 Br 0.55 Cl 0.45 has been analysed, for temperatures in the range 0-500 K, on the assumption that can be expressed as the sum of the terms ( C p — C v ), C (lat.), C (lib.), C (int.) and C (extra); C (lat.), C (lib.) and C (int.) are respectively, the contributions from the lattice vibrations (phonons), and the librations (torsional oscillations) and internal vibrations of the ammonium ions. C (extra) is the contribution from order-disorder changes or any other ‘abnormal’ sources. The analysis requires a knowledge of certain thermodynamic and spectroscopic properties of the crystals, and current information on these has been surveyed. The ‘normal ’ or ‘baseline’ heat capacity C´ p for the three solids has been estimated; C´ p is the molar heat capacity to be expected from the progressive excitation of the lattice vibrations, torsional oscillations and internal vibration of the cations, and from the expansion of the lattice. By comparing C´ p and the observed heat capacity C p , C (extra) has been evaluated, making it possible to examine the development with rising temperature of the configurational or otherwise ‘extra’ entropy. The main results emerging from this are the following, ( a ) For all three solids, the entropy gain at the λ-transition (or at the two lower transitions, taken together, in ammonium bromide) is not about R ln 2, as has often been stated, but is roughly 50 % larger. The excess over R ln 2 is to be attributed to changes in the phonon spectrum and to a reduction in the frequency of the torsional oscillations of the ammonium ions, ( b ) The heat capacity of the β-phase of all three solids is abnormally large. Possible reasons for this are briefly discussed, but a definitive explanation is lacking. ( c ) The overall entropy gain for all three solids when the high-temperature face-centred a-phase has been formed is considerably greater than R In 6, the configurational contribution to be expected from the structural evidence that each ammonium ion in this phase has access to six distinguishable orientations. The balance is believed to be due to enhanced freedom of torsional movement of the ammonium ions, which must be a complex motion. However, from its observable thermodynamic consequences, this motion is still far from true free rotation.

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