MATERIALS THERMODYNAMICS II

Chapter 7 PHASE EQUILIBRIUM IN A ONE COMPONENT SYSTEM

Thermodynamic Properties of a System

1. Extensive Properties, which are additive. Mass, volume, energy, etc. 2. Intensive Properties, to which a value may be assigned at each point in the system. Temperature, pressure, chemical potential, etc.

Intensive Properties Temperature: Measure of the tendency for heat to leave the system. Pressure: Measure of the potential of a system to undergo massive movement by expansion or contraction. Chemical potential: Measure of the rate of energy change of a system with the change in the amount of ith component where all other variables being held constant.

Complete thermodynamic equilibrium is said to prevail when the system under consideration is in mechanical (pressure is same at all points), thermal (no temperature gradient) and chemical equilibrium (Gibbs chemical potential of each component must be equal).
In a closed system of fixed composition, e.g., a one-component system, equilibrium, at the temperature, T, and the pressure, P, occurs when the system exists in that state which has the minimum value of G.

The Gibbs free energy of the system, G, is independent of the proportions of the ice phase and the water phase present. at const. T&P

The chemical potential of species in a particular state equals the molar Gibbs free energy of the species in that particular state. (P =1 atm, T = 273 K)

If P=1 atm and T > 273 K,

T < 273 K,

2 () < 2 ()
2 () > 2 ()

Hesss Law

G=H-TS At all T, H(l) > H(s) S(l) > S(s) So solid will be stable at all T. However, G=H-TS Therefore, at T < Tm, H(sl) > TS(sl) whereas at T > Tm, H(sl) < TS(sl)
273 T (K)

Joules

Variation of G with P at Constant T

Const T (273 K)

For water: V(s) > V(l)

1 atm

G as a Function of T & P
For equilibrium to be maintained: G(l) = G(s) dG(l) = dG(s) V(l) dP - S(l) dT = V(s) dP - S(s) dT

() ()

Clapeyron eqn.

V < 0 for H2O and H>0 for all materials:

<0

T P
0 C, 1 atm

0.0075 C , 0.006 atm

Equilibrium between vapor phase and a condensed phase

Vvapor >> Vcond.phase

V Vvapor

Assuming vapor behave as ideal gas: =

= 2 dlnP = 2

Clasius-Clapeyron eqn.

 If H is independent from T: cp(vapor) = cp(cond.phase) = + . If Cp 0, but independent of T: Cp = const.

= 298 +

298 298 + = 2 298 298 1 = + + . = + +

298

= 298 + 298

For H2O: ,2 () =30+10.7 10-3T+0.33 105T-2 J/K (298-2500 K)

,2 () =75.44 J/K (273-373 K)

. = 41,090 J

, = ,373 +

373

()

5 0.3310 =57,383-45.44T+5.35x10-3T2

dlnP =

and R-8.314 J/K mole

6,901.64 1,984.509 4 = 5.465 + 6.435 10 + 2 + . Since the normal boiling point of the liquid is defined as the temperature at which the saturated vapor pressure exerted by the liquid is 1 atm, P=1 atm at 373K. const=50.62

Thus the variation of the saturated vapor pressure of water with T in the range 273-373K: 2997 862 3 = 5.465 + 0.279 10 + 2 + 21.98

A B m 1 b

Pressure (atm)

solid C
0.006 B O A

liquid

vapor

C 0 0.0075 100

Temperature (C)

Gibbs Phase Rule

Single phase areas have two degrees of freedom since T and P can be altered independently without disturbing the equilibrium. While the equilibrium through AO , BO , and CO lines, which indicates two phase equilibrium, can be maintained by changing only one variable, either T or P. Therefore, they have only one degree of freedom. On the other hand, tripoint junction has zero degrees of freedom. These criteria result in the Gibbs phase rule: F=C-P+2 Taking F=0 gives the maximum number of phases that can be observed for a given number of species.

P1

s a o b

G Since T P,comp

= S :

all of the slopes are negative

v

and since S(v) > S(l) > S(s) :

T
v l s

slopes are increasing from solid to vapor.

SKETCH G-P DIAGRAM FOR GIVEN T WITH THE BLUE COLOR LINE!!!
T

Example Problem 1 The vapor pressure of solid NaF varies with temperature as 34,450 lnP atm = 2.01 lnT + 33.74 T and the vapor pressure of liquid NaF varies with temperature as 31,090 lnP atm = 2.52 lnT + 34.66 T Calculate the the normal boiling temperature of NaF. The normal boiling temperature,Tb , is defined as that temperature at which the saturated vapor pressure of the liquid is 1 atm. 31,090 ln 1 = 0 = 2.52 lnT + 34.66 T Tb = 2006K

 Calculate the temperature and pressure at the triple point. The saturated vapor pressures for the solid and liquid phases intersect at the triple point, Ttp .
34,450 31,090 2.01 lnTtp + 33.74 = 2.52 lnTtp + 34.66 Ttp Ttp Ttp = 1239K The pressure at the triple point can be calculated either from the vapor pressure of solid or vapor pressure of liquid equation. 34,450 Ptp = exp 2.01 ln1239 + 33.74 1239 Ptp = 2.29 1024 atm

 Calculate the molar heat of evaporation of NaF at its normal boiling temperature. For vapor in equilibrium with liquid: 31,090 lnP atm = 2.52 lnT + 34.66 T From Clasius-Clapeyron equation: dlnP H 31,090 2.52 = = 2 2 dT RT T T
Since R=8,314 J/molK and Tb is 2006 K: H = 31,090 8.314 2.52 8.314 2006 H = 216,500 J

 Calculate the molar heat of melting of NaF at the triple point. For vapor in equilibrium with solid: 34,450 lnP atm = 2.01 lnT + 33.74 T From the previous case,we know that: H(lv) = 31,090 8.314 2.52 8.314 T
And it is obvious that: H(sv) = 34,450 8.314 2.01 8.314 T Since H(sl) + H(lv) = H(sv) : H(sl) = 27,900 + 4.24T Since Ttp = 1239 K:

H(sl) = 33,150J

 Calculate the difference between the constant-pressure molar heat capacities of liquid and solid NaF. As we know = ()
Since H(sl) = 27,900 + 4.24T: () = ()

= 4.24 /K

Example Problem 2 The vapor pressures of zinc have been written as 15,780 lnP atm = 0.755 lnT + 19.25 T 15,250 lnP atm = 1.255 lnT + 21.79 T Which of the two equations is for solid zinc?

Example Problem 3 Below the triple point (-56.2C) the vapor pressure of solid CO2 is given as: 3116 lnP atm = + 16.01 T The molar latent heat of melting of CO2 is 8330 J and normal melting temperature of CO2 is -57 C. Calculate the vapor pressure exerted by liquid CO2 at 25 C and explain why solid CO2 is referred to as dry ice.

Homework Carbon has three allotropes: graphite, diamond, and a metallic form called solid III. Graphite is the stable form of 298 K and 1 atm pressure, and increasing the pressure on graphite at temperatures less than 1440 K causes the transformation of graphite to diamond and then the transformation of diamond to solid III. Calculate the pressure which, when applied to graphite at 298 K, causes the transformation of graphite to diamond. Given: H298 K(Graphite) H298 K Diamond = 1900J S298 K(Graphite) = 5.74 J/K S298 K(Diamond) = 2.37J/K 298 K(Graphite) = 2.22 g/cm3 298 K(Diamond) = 3.515 g/cm3