The methods of this section can also be applied to reactions in which one set of solids converts to another. A geologically important example is the transformation of albite into jadeite + quartz:

NaAlSi3O8NaAlSi2O6+SiO2

Use the data at the back of this book to determine the temperatures and pressures under which a combination of jadeite and quartz is more stable than albite. Sketch the phase diagram of this system. For simplicity, neglect the temperature and pressure dependence of both S and V.

Short Answer

Expert verified

The temperature is 100 K above room temperature, an extra 1.7 kbar of pressure is required to keep Jadeite+Quartz stable.

Step by step solution

01

Given information

The Gibbs free energy, Entropy and Molar Volumes for Albite, Jadeite, quartz is given as:

AlbiteGa=-3711.5KJSa=204.4J/KVa=100.07cm3JadeiteGj=-2852·1KJSj=133·5J/KVj=60·40cm3QuartzGq=-856.64KJSq=41·84J/KVq=22·69cm3

Albitejadeite+quartz

For the above reaction

role="math" localid="1646935903662" ΔG=Gfinal-Ginitial=Gj+Gq-Ga=(-2852·1-856·64+3711·5)kJ=2·76kJ>0

02

Explanation

As a result, under normal settings, the Albite is more stable.

At high pressures, the jadeite + quartz combination becomes more stable.

The change in volume is calculated as

ΔV=Va-Vj-Vq=(100·07-60·40-22·69)cm3=16·98cm3=1.698×10-5m31kJkbar=10-5m3ΔV=1·698kJkbar

03

Explanation

At standard temperatures, the pressure at which jadeite + quartz becomes stable is:

P=ΔGΔVP=2·761·698KJKJKbarP=1.6254Kbar

The coexistence line with the P-axis in the P-T diagram is thus of relevance.

The Clausius-Clapeyron equation's slope is

dPdT=ΔSΔVΔS=Sa-Sj-Sq=(204·4-133·5-41·84)J/KΔS=29·06J/KSlope=ΔSΔV=29·06J/K1·698J/bar=17·11barK

04

Conclusion

The phase diagram for Jadeite+Quartz and Albite is

Jadeite+Quartz is stable at pressures more than 1.6254kbar at room temperature. The Jadeite& Quartz-Albite phase border has a slope of 17.11 bar/K.

If the temperature is 100 K above room temperature, an extra 1.7 kbar of pressure is required to keep Jadeite+Quartz stable.

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Most popular questions from this chapter

Consider again the aluminosilicate system treated in Problem 5.29. Calculate the slopes of all three phase boundaries for this system: kyanite andalusite, kyanite-sillimanite, and andalusite-sillimanite. Sketch the phase diagram, and calculate the temperature and pressure of the triple point.

What happens when you spread salt crystals over an icy sidewalk? Why is this procedure rarely used in very cold climates?

The first excited energy level of a hydrogen atom has an energy of 10.2 eV, if we take the ground-state energy to be zero. However, the first excited level is really four independent states, all with the same energy. We can therefore assign it an entropy of S=kln4, since for this given value of the energy, the multiplicity is 4. Question: For what temperatures is the Helmholtz free energy of a hydrogen atom in the first excited level positive, and for what temperatures is it negative? (Comment: When F for the level is negative, the atom will spontaneously go from the ground state into that level, since F=0 for the ground state and F always tends to decrease. However, for a system this small, the conclusion is only a probabilistic statement; random fluctuations will be very significant.)

Consider a completely miscible two-component system whose overall composition is x, at a temperature where liquid and gas phases coexist. The composition of the gas phase at this temperature is xaand the composition of the liquid phase is xb. Prove the lever rule, which says that the proportion of liquid to gas is x-xa/xb-x. Interpret this rule graphically on a phase diagram.

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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