Warning: foreach() argument must be of type array|object, bool given in /var/www/html/web/app/themes/studypress-core-theme/template-parts/header/mobile-offcanvas.php on line 20

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

GT=-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.

Unlock Step-by-Step Solutions & Ace Your Exams!

  • Full Textbook Solutions

    Get detailed explanations and key concepts

  • Unlimited Al creation

    Al flashcards, explanations, exams and more...

  • Ads-free access

    To over 500 millions flashcards

  • Money-back guarantee

    We refund you if you fail your exam.

Over 30 million students worldwide already upgrade their learning with Vaia!

One App. One Place for Learning.

All the tools & learning materials you need for study success - in one app.

Get started for free

Most popular questions from this chapter

Problem 5.58. In this problem you will model the mixing energy of a mixture in a relatively simple way, in order to relate the existence of a solubility gap to molecular behaviour. Consider a mixture of A and B molecules that is ideal in every way but one: The potential energy due to the interaction of neighbouring molecules depends upon whether the molecules are like or unlike. Let n be the average number of nearest neighbours of any given molecule (perhaps 6 or 8 or 10). Let n be the average potential energy associated with the interaction between neighbouring molecules that are the same (4-A or B-B), and let uAB be the potential energy associated with the interaction of a neighbouring unlike pair (4-B). There are no interactions beyond the range of the nearest neighbours; the values of μoandμABare independent of the amounts of A and B; and the entropy of mixing is the same as for an ideal solution.

(a) Show that when the system is unmixed, the total potential energy due to neighbor-neighbor interactions is 12Nnu0. (Hint: Be sure to count each neighbouring pair only once.)

(b) Find a formula for the total potential energy when the system is mixed, in terms of x, the fraction of B.

(c) Subtract the results of parts (a) and (b) to obtain the change in energy upon mixing. Simplify the result as much as possible; you should obtain an expression proportional to x(1-x). Sketch this function vs. x, for both possible signs of uAB-u0.

(d) Show that the slope of the mixing energy function is finite at both end- points, unlike the slope of the mixing entropy function.

(e) For the case uAB>u0, plot a graph of the Gibbs free energy of this system

vs. x at several temperatures. Discuss the implications.

(f) Find an expression for the maximum temperature at which this system has

a solubility gap.

(g) Make a very rough estimate of uAB-u0for a liquid mixture that has a

solubility gap below 100°C.

(h) Use a computer to plot the phase diagram (T vs. x) for this system.

Consider the production of ammonia from nitrogen and hydrogen,

N2 + 3H2 2NH3
at 298 K and 1 bar. From the values of Hand S tabulated at the back of this book, compute Gfor this reaction and check that it is consistent with the value given in the table.

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,
VUS=SUV

where each /Vis taken with S fixed, each/S is taken with V fixed, and N is always held fixed. From the thermodynamic identity (for U ) you can evaluate the partial derivatives in parentheses to obtain

TVS=-PSV

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, and G ). 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.


When solid quartz "dissolves" in water, it combines with water molecules in the reaction

SiO2(s)+2H2O(l)H4SiO4(aq)

(a) Use this data in the back of this book to compute the amount of silica dissolved in water in equilibrium with solid quartz, at 25° C

(b) Use the van't Hoff equation (Problem 5.85) to compute the amount of silica dissolved in water in equilibrium with solid quartz at 100°C.

Sketch qualitatively accurate graphs of Gvs.Tfor the three phases ofH2O(ice, water, and steam) at atmospheric pressure. Put all three graphs on the same set of axes, and label the temperatures0°Cand 100°C. How would the graphs differ at a pressure of0.001bar?

See all solutions

Recommended explanations on Physics Textbooks

View all explanations

What do you think about this solution?

We value your feedback to improve our textbook solutions.

Study anywhere. Anytime. Across all devices.

Sign-up for free