equilibrium

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equilibrium

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-Temperature Dependence -Pressure Dependence

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Usually, only one phase of a given substance is stable at any given temperature and pressure. At some conditions of temperature and pressure, two or more phases may exist in equilibrium. A slight change in temperature or pressure will favor one phase over others. The conversion of one phase to another is a phase transition. Phase transitions occur with a decrease (spont.) or no change (equil.) in Gibbs energy.

Example Problem

The standard Gibbs energy of formation of metallic white tin (a-tin) is 0 at 25 oC and that of nonmetallic gray tin (b-tin) is +0.13 kJ mol-1 at the same temperature. Which is the thermodynamically stable phase at 25 oC? Solution: The thermodynamically stable phase is the one with the lower Gibbs energy, which would be the a- (white) tin at 25 oC.

Note: At lower temperatures, the nonmetallic gray tin becomes the stable form. The transition is known among metallurgists as the tin disease.

This is similar to how Fig. 5.1 should have looked. (Mm/MT)p = (MGm/MT)p = -Sm

The straight lines show that S is approx. constant with temp. (Really, they curve.)

Since S is positive for all phases of all substances, the slopes are all negative. Note that the gas phase has the steepest slope; the solid phase, the least steep.

At left is a generic p-T phase diagram. For any of the phase boundary lines , the slope is given by dp/dT = DS/DV = DH/TDV

For the transitions s->l, l->g, and s->g, DS > 0 For l->g and s->g, DV > 0, while for s->l, DV is almost always > 0 This explains the positive slopes.

A one-component phase diagram represents the situation when only that component is present. Thus the vapor-pressure curve plots the pressure ONLY of the vapor (no air) Water filling a container at 50 torr WILL NOT EVAPORATE. If some of the liquid is removed without decreasing the size of the container (or letting any air in) vapor will form in the space above the liquid until the pressure of the vapor reaches the equilibrium vapor pressure (left).

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Example Problem

What is the minimum pressure at which liquid is the thermodynamically stable phase of water at 25 oC? Solution: Start in the liquid region of the phase diagram for water at 25 oC and drop down in pressure until the vapor pressure line is reached. This occurs at 23.8 torr. Below this pressure liquid water cannot exist at 25 oC .

Criteria of Equilibrium

At equilibrium, the chemical potential of a substance is the same throughout a sample, regardless of how many phases are present.

Temperature Dependence

(Mm/MT)p = -Sm As the temperature is raised, the chemical potential of a pure substance decreases, always. When a phase transition occurs, the relative values of the chemical potentials of the various phases are modified.

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(Mm/Mp)T = Vm. The greater the molar volume, the more steeply m rises with pressure.

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(a) and (b) in the figure at left show two ways of determining the effect of applied pressure on vapor pressures. For a perfect gas,

p = p* exp[VmDp/RT] shows how the vapor pressure increases when the applied pressure increases.

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ma(p,T) = mb(p,T)

dm = -SmdT + Vmdp

-Sa,mdT + Va,m dp = -Sb,mdT + Vb,mdp (Vb,m - Va,m)dp = (Sb,m - Sa,m)dT dp/dT = DtrsS/DtrsV

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dp/dT = DS/DV = DH/TDV (the Clapeyron equation) applies to any two phases a and b. For instance, in melting, dp/dT = DfusH/TDfusV If DH and DV are approx. constant,

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The Clausius-Clapeyron equation applies the Clapeyron equation to the special case where phase b is the gas phase, and the gas is assumed perfect. dp/dT = DvapH/TVg = DvapH/T(RT/p) d(ln p)/dT = DH/RT2 ln p2 = ln p1 + DH 1 - 1 R T1 T2 If p is known at one temp it can be found at another temp.

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For sublimation, substitute DsubH for DvapH The assumptions/ approximations are: DV . Vg and Vg . RT/p

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Determining p at a Given T How do you arrive at the value 23.8 torr for the vapor

Read it off a p-T phase diagram (if a diagram that can be read to that precision is available). Look in a handbook or other reference for vapor pressure tables for water. Calculate from a known vapor pressure at some other temperature (C-C eqn, see next slide). Calculate from DG value for the liquid-to-gas transition. From the Table 2.6, DfGo = -228.57 kJ/mol for gaseous water at 25 oC and -237.13 kJ/mol for liquid water at 25 oC. Therefore DtrGo = + 8.56 kJ/mol for vapn of water at 25 oC. From DtrGo can be found Ktr , since DtrGo = - RT ln Ktr = This gives ln Ktr = (+8.56 kJ/mol)/(-2.479 kJ/mol) = -3.453 Therefore Ktr = 0.0317 But for a vapn rxn, Ktr is simply equal to p/po (po = 1 bar) So we arrive at p = 0.0317 bar = 3.17 kPa = 23.8 torr 17

Phase Rule

where C = the number of components (1 so far in this chapter), P = the number of phases present, and F = the number of degrees of freedom (the

number of intensive variables such as temp, pres, or mol frac that can be changed without disturbing the number of phases in equilibrium)

For a one-component system the phase rule becomes F = 3 - P When only one phase is present both p and T are independently variable. (An area on the p-T diagram) When two phases are present there is only one p possible for a given T. (A line on the p-T diagram) Three phases can be present (triple point) but there is no variation allowed in p or T.

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Most functions (volume, enthalpy, entropy) change discontinuously at a phase transition. A few (chemical potential) change continuously. Cp goes 4 and back.

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The previous slide illustrated first-order phase transitions, in which the chemical potential was a continuous function with a discontinuous first derivative. A second-order transition is one in which the first derivative of m with respect to temperature is continuous but the second derivation is discontinuous.

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Lambda Transition

The transition shown at left is that of the fluidsuperfluid transition in liquid helium. It is named for the shape of the heat capacity curve.

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Surface Tension

Surface tension, or surface energy, is the force per unit length (along h) or energy per unit area to increase the surface area of a liquid.

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The pressure on the concave side of an interface, pin is always greater than the pressure on the convex side, pout. pin = pout + 2g/r

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Capillary Rise

p = rgh

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