Figure 5.35 (left) shows the free energy curves at one particular temperature for a two-component system that has three possible solid phases (crystal structures), one of essentially pure A, one of essentially pure B, and one of intermediate composition. Draw tangent lines to determine which phases are present at which values of x. To determine qualitatively what happens at other temperatures, you can simply shift the liquid free energy curve up or down (since the entropy of the liquid is larger than that of any solid). Do so, and construct a qualitative phase diagram for this system. You should find two eutectic points. Examples of systems with this behaviour include water + ethylene glycol and tin - magnesium.

Short Answer

Expert verified

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

Step by step solution

01

Given information

The free energy curves at one particular temperature for a two-component system that has three possible solid phases (crystal structures), one of essentially pure A, one of essentially pure B, and one of intermediate composition.

02

Step 2: 

Consider the Gibbs free energy graph below, which shows a system with three solid phases: α,βandγ. One 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 αphase 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 by

G=U-TS+PV

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

role="math" localid="1647065790638" 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 β vanish. When we lower the temperature, the stability of γ plus the liquid appears, as seen in the previous figure for large x. As the temperature drops, the liquid's stable range narrows until it vanishes at two locations, which are known as the eutectic points (where all the liquid freezes).

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Most popular questions from this chapter

The standard enthalpy change upon dissolving one mole of oxygen at 25°C is -11.7 kJ. Use this number and the van't Hoff equation (Problem 5.85) to calculate the equilibrium (Henry's law) constant for oxygen in water at 0°C and at 100° C. Discuss the results briefly.

The partial-derivative relations derived in Problems 1.46,3.33, and 5.12, plus a bit more partial-derivative trickery, can be used to derive a completely general relation between CPandCV.

(a) With the heat capacity expressions from Problem 3.33 in mind, first considerSto be a function of TandV.Expand dSin terms of the partial derivatives (S/T)Vand (S/V)T. Note that one of these derivatives is related toCV

(b) To bring in CP, considerlocalid="1648430264419" Vto be a function ofTand P and expand dV in terms of partial derivatives in a similar way. Plug this expression for dV into the result of part (a), then set dP=0and note that you have derived a nontrivial expression for (S/T)P. This derivative is related to CP, so you now have a formula for the difference CP-CV

(c) Write the remaining partial derivatives in terms of measurable quantities using a Maxwell relation and the result of Problem 1.46. Your final result should be

CP=CV+TVβ2κT

(d) Check that this formula gives the correct value of CP-CVfor an ideal gas.

(e) Use this formula to argue that CPcannot be less than CV.

(f) Use the data in Problem 1.46 to evaluateCP-CVfor water and for mercury at room temperature. By what percentage do the two heat capacities differ?

(g) Figure 1.14 shows measured values of CPfor three elemental solids, compared to predicted values of CV. It turns out that a graph of βvs.T for a solid has same general appearance as a graph of heat capacity. Use this fact to explain why CPand CVagree at low temperatures but diverge in the way they do at higher temperatures.

Consider an ideal mixture of just 100 molecules, varying in com- position from pure A to pure B. Use a computer to calculate the mixing entropy as a function of NA, and plot this function (in units of k). Suppose you start with all A and then convert one molecule to type B; by how much does the entropy increase? By how much does the entropy increase when you convert a second molecule, and then a third, from A to B? Discuss.

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.

In this problem you will investigate the behavior of a van der Waals fluid near the critical point. It is easiest to work in terms of reduced variables throughout.

(a) Expand the van der Waals equation in a Taylor series in , keeping terms through order . Argue that, for T sufficiently close to Tc, the term quadratic in (V-VC)becomes negligible compared to the others and may be dropped.

(b) The resulting expression for P(V) is antisymmetric about the point V = Ve. Use this fact to find an approximate formula for the vapor pressure as a function of temperature. (You may find it helpful to plot the isotherm.) Evaluate the slope of the phase boundary,dP/dT

( c) Still working in the same limit, find an expression for the difference in volume between the gas and liquid phases at the vapor pressure. You should find Vg-VlTc-Tβ.8, where (3 is known as a critical exponent. Experiments show that (3 has a universal value of about 1/3, but the van der Waals model predicts a larger value.

(d) Use the previous result to calculate the predicted latent heat of the transformation as a function of temperature, and sketch this function.

The shape of the T = Tc isotherm defines another critical exponent, called P-PcV-VcδCalculate 5 in the van der Waals model. (Experimental values of 5 are typically around 4 or 5.)

A third critical exponent describes the temperature dependence of the isothermal compressibility, K=-t This quantity diverges at the critical point, in proportion to a power of (T-Tc) that in principle could differ depending on whether one approaches the critical point from above or below. Therefore the critical exponents 'Y and -y' are defined by the relations

κT-Tc-γTc-T-γ'

Calculate K on both sides of the critical point in the van der Waals model, and show that 'Y = -y' in this model.

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