Order-disorder phase transition continuous

Some surfaces of bcc metals, such as W(100) or Mo(100), reconstruct [28], The reconstruction occurs reversibly upon cooling the crystals below 200-250 K, and it can be viewed as a continuous, temperature-driven, order-disorder phase transition. The room temperature phase is (1 x 1) and the low temperature phase has a c(2 x 2)p2mg unit cell involving only short-range atomic displacements [29]. Much has been speculated with respect to the role of surface states in driving this reconstructions, but no clear evidence has been presented so far [30]. 

The transition from the room temperature (2x1) phase to ground state c(4x2) is described by an order-disorder phase transition at about = 200 K [23]. No mass transport or bond breaking is necessary for this transition. The order parameter - that is, the area covered with c(4x2) reconstruction - increased smoothly from zero at high temperatures to one when the temperature is lowered. This behavior of a continuous (second order) phase transition varies as (1 — T /Tc) for the temperature T near the transition temperature as shown in Figure 9.18. 

FIG. 14 Phase diagram of the quantum APR model in the Q -T plane. The solid curve shows the line of continuous phase transitions from an ordered phase at low temperatures and small rotational constants to a disordered phase according to the mean-field approximation. The symbols show the transitions found by the finite-size scaling analysis of the path integral Monte Carlo data. The dashed line connecting these data is for visual help only. (Reprinted with permission from Ref. 328, Fig. 2. 1997, American Physical Society.)... 

Even when complete miscibility is possible in the solid state, ordered structures will be favored at suitable compositions if the atoms have different sizes. For example copper atoms are smaller than gold atoms (radii 127.8 and 144.2 pm) copper and gold form mixed crystals of any composition, but ordered alloys are formed with the compositions AuCu and AuCu3 (Fig. 15.1). The degree of order is temperature dependent with increasing temperatures the order decreases continuously. Therefore, there is no phase transition with a well-defined transition temperature. This can be seen in the temperature dependence of the specific heat (Fig. 15.2). Because of the form of the curve, this kind of order-disorder transformation is also called a A type transformation it is observed in many solid-state transformations. 

Fig. 35 Phase diagrams AB miktoarm-star copolymers for n = 2, n = 3, n = 4 and n = 5. mean-field critical point through which system can transition from disordered state to Lam phase via continuous, second-order phase transition. All other phase transitions are first-order. From [112]. Copyright 2004 American Chemical Society...

A second-order phase transition is one in which the enthalpy and first derivatives are continuous, but the second derivatives are discontinuous. The Cp versus T curve is often shaped like the Greek letter X. Hence, these transitions are also called -transitions (Figure 2-15b Thompson and Perkins, 1981). The structure change is minor in second-order phase transitions, such as the rotation of bonds and order-disorder of some ions. Examples include melt to glass transition, X-transition in fayalite, and magnetic transitions. Second-order phase transitions often do not require nucleation and are rapid. On some characteristics, these transitions may be viewed as a homogeneous reaction or many simultaneous homogeneous reactions. 

Symmetry is represented by the elements of a (mathematical) group and thus cannot change continuously. The a-0 phase transition therefore occurs at a distinct temperature. Let us now assume that we have identified an extensive thermodynamic variable which can distinguish states between the a and 0 phases. We call it an order parameter (/ ). For a quantitative description of order-disorder or continuous displacive processes, the order parameter is normalized (0< s 1). For example, if we regard the classic 0-0 brass transition, tj is defined as (2/Cu -1), where /Cu is the fraction of Cu atoms which occupy the (0,0,0) sites of the (Cu,Zn) bcc structure. 

Fig. 6.36 Phase diagram calculated using SCFT for a blend of a symmetric diblock with a homopolymer with fl = 1 (see Fig. 6.32 for a blend with a diblock with / = 0.45) as a function of the copolymer volume fraction

Chapters 13 and 14 use thermodynamics to describe and predict phase equilibria. Chapter 13 limits the discussion to pure substances. Distinctions are made between first-order and continuous phase transitions, and examples are given of different types of continuous transitions, including the (liquid + gas) critical phase transition, order-disorder transitions involving position disorder, rotational disorder, and magnetic effects the helium normal-superfluid transition and conductor-superconductor transitions. Modem theories of phase transitions are described that show the parallel properties of the different types of continuous transitions, and demonstrate how these properties can be described with a general set of critical exponents. This discussion is an attempt to present to chemists the exciting advances made in the area of theories of phase transitions that is often relegated to physics tests. 

The experimental results in Figure 2 and Table II clearly show three qualitatively different behaviors an abrupt order-disorder transition a relatively rapid continuous transition and a gradual, smooth ordering of the polymer backbone. These observations are qualitatively identical to the three possible phase behaviors predicted by the theory. Moreover, a degree of quantitative understanding can be obtained. 

Abstract. - High-resolution powder neutron diffraction has been used to study the crystal structure of the fullerene Cm in the temperature range 5 K to 320 K. Solid Cm adopts a cubic structure at all temperatures. The experimental data provide clear evidence of a continuous phase transition at ca. 90 K and confirm the existence of a first-order phase transition at 260 K. In the high-temperature face-centred-cubic phase (T > 260 K), the Cm molecules are completely orientation-ally disordered, undergoing continuous reorientation. Below 260 K, interpretation of the diffraction data is consistent with uniaxial jump reorientation principally about a single (111) direction. In the lowest-temperature phase (T < 90 K), rotational motion is frozen although a small amount of static disorder still persists. 

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