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Repeat the previous problem for the diagram in Figure 5.35 (right), which has an important qualitative difference. In this phase diagram, you should find that β and liquid are in equilibrium only at temperatures below the point where the liquid is in equilibrium with infinitesimal amounts of αandβ . This point is called a peritectic point. Examples of systems with this behaviour include water + NaCl and leucite + quartz.

Short Answer

Expert verified

Starting at x=0 on the left, theαphase and the liquid phase are stable, then the liquid phase is stable, then the β phase and the liquid phase are stable, then a narrow range of x where only the βphase is stable, and ultimately just the liquid phase is stable.

Step by step solution

01

Given information

βand liquid are in equilibrium only at temperatures below the point where the liquid is in equilibrium with infinitesimal amounts of α and β . This point is called a peritectic point.

02

Explanation

Consider the Gibbs free energy graph below, which shows a system with three solid phases: α,βandγOne is a pure A substance, one is a pure B substance, and one is a mixture of the two.

03

Explanation

First, as shown in the diagram, we draw three tangent lines from left to right: first, the a phase plus the liquid phase are stable, then the liquid phase is stable, then the βphase plus the liquid phase are stable, then a narrow range of x where only the βphase is stable, and finally only the liquid phase is stable.

04

Calculations

The Gibbs free energy is given as:

G=U-TS+PV

At constant entropy and constant pressure, differentiate the Gibbs free energy to get:

dG=dU-SdT+PdV

By increasing the temperature

∂G∂T=-S

We can see from this equation that as the temperature rises, the stability ranges of αand βvanish. When we lower the temperature, the stability of γplus the liquid appears, as shown in the preceding figure for large x. As the temperature drops, the liquid's stable range narrows until it evaporates at two locations, one of which is known as the eutectic point (at which all the liquid freezes). Only at temperatures below the red point, where the liquid is in equilibrium with tiny amounts of αand β and the liquid in equilibrium. This point is known as the peritectic point.

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Most popular questions from this chapter

Osmotic pressure measurements can be used to determine the molecular weights of large molecules such as proteins. For a solution of large molecules to qualify as "dilute," its molar concentration must be very low and hence the osmotic pressure can be too small to measure accurately. For this reason, the usual procedure is to measure the osmotic pressure at a variety of concentrations, then extrapolate the results to the limit of zero concentration. Here are some data for the protein hemoglobin dissolved in water at 3oC:

Concentration (grams/liter)∆h (cm)
5.62.0
16.66.5
32.512.8
43.417.6
54.022.6

The quantity ∆his the equilibrium difference in fluid level between the solution and the pure solvent,. From these measurements, determine the approximate molecular weight of hemoglobin (in grams per mole).

An experimental arrangement for measuring osmotic pressure. Solvent flows across the membrane from left to right until the difference in fluid level,∆h, is just enough to supply the osmotic pressure.

Compare expression 5.68 for the Gibbs free energy of a dilute solution to expression 5.61 for the Gibbs free energy of an ideal mixture. Under what circumstances should these two expressions agree? Show that they do agree under these circumstances, and identify the function f(T, P) in this case.

Express ∂ΔG°/∂Pin terms of the volumes of solutions of reactants and products, for a chemical reaction of dilute solutes. Plug in some reasonable numbers, to show that a pressure increase of 1 atm has only a negligible effect on the equilibrium constant.

Let the system be one mole of argon gas at room temperature and atmospheric pressure. Compute the total energy (kinetic only, neglecting atomic rest energies), entropy, enthalpy, Helmholtz free energy, and Gibbs free energy. Express all answers in SI units.

Functions encountered in physics are generally well enough behaved that their mixed partial derivatives do not depend on which derivative is taken first. Therefore, for instance,

∂∂V∂U∂S=∂∂S∂U∂V

where each ∂/∂Vis taken with Sfixed, each ∂/∂Sis taken with Vfixed, and Nis always held fixed. From the thermodynamic identity (forU) you can evaluate the partial derivatives in parentheses to obtain

∂T∂VS=-∂P∂SV

a nontrivial identity called a Maxwell relation. Go through the derivation of this relation step by step. Then derive an analogous Maxwell relation from each of the other three thermodynamic identities discussed in the text (for H,F,andG ). Hold N fixed in all the partial derivatives; other Maxwell relations can be derived by considering partial derivatives with respect to N, but after you've done four of them the novelty begins to wear off. For applications of these Maxwell relations, see the next four problems.

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