Unitary Heterogeneous System

One Component System

3D View

186 Introduction to the Thermodynamics of Materials

Figure 7.8 Schematic representation of the equilibrium surfaces of the

solid and liquid phases of water in G-T-P space.
10/20/16 surface in G-T-P space, and the line along
MSE which
513 Xuthe surfaces intersect represents the
variation of P with T required for maintenance of the equilibrium between the two

H2O Phase Diagram

http://ch302.cm.utexas.edu/physEQ/physical/physical-all.php

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A Different View

Phase Equilibrium in a One-Component System

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193

Calculation of Unary Phase

Diagram
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)u
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YA pY!A g Y! \ 2YAb\2!_ pgAd\!_ J!2A8 6 Sq 7q b! )A
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2u !d\\gd AbpA!A8 YA! !d: g_bA 2Y!dQA Jg !d\\gd ! j !b
g ! gYA pA2\K2 2gd:\\gd g Y! YA A_!\A pg\\gd gJ YA 2YAb\2!_
pgAd\!_ J!2A b! )A KA:

10/20/16

MSE 513 Xu


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Parameter Dependence on T and P

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Phase Diagram of Carbon

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Phase Equilibrium in a One-Component System

185

Gibbs Free Energy as a Function of

T and P
From Eq. (5.12)

and

Thus, for equilibrium to be maintained between the two phases,

or

At equilibrium G=0, and hence H=T S, substitution of which into the above equation
gives

Eq. (7.5), which is known as the Clapeyron equation, gives the required relationships
equation
between the variations of Clapeyron
temperature and
pressure which are required for the
maintenance of equilibrium between the two phases.
10/20/16 The value of

(dP/dT)

V(sl) for H2O is negative

and513 H
for all materials is positive. Thus
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(sl)

for H O is negative, i.e., an increase in pressure decreases the equilibrium


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EQUILIBRIUM BETWEEN THE VAPOR

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rearrangement of which gives

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(7.6)

(7.6)

!d:
Eq. (7.6) is known as the Clausius-Clapeyron equation.
 of temperature, equation.

(condensed phase),
If is H
is independent
i.e., if Cp(vapor)=C
Eq. (7.6)
known
as the Clausius-Clapeyron
p




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phase),
If integration
H is independent
of temperature,
i.e.,rif Cp(vapor)=Cp(condensedSJe7
of Eq. (7.6)_d
gives

integration of Eq. (7.6) gives

(7.7)
Y\ ApA\gd pA:\2 Y!8 \J YA !pg pAA \d Az\_\)\b \Y ! 2gd:AdA:
pY!A \ bA!A: ! ! A\A gJ AbpA!A8 ! p_g gJ YA _gQ!\Yb gJ YA !pg
(7.7)
pAA u
YA
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YA
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Az!_ g r
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p_g Jgvapor
b!d
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A_AbAdu
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value of P\QA
at any
Tu
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pressure
This
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2AAsg)A
Y\
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!
pAA
j !bu
YA
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gd exerted
bg
phase
at the
temperature
T. Eq.
(7.7) thus)A_g
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that
the saturated
vapor
pressure
equilibrium
is maintained
between
the
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the
condensed
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by a ApAAd
exponentially
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value
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the saturated
vapor
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in Sec. 5.3. If

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Alternative View (Copper)

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10/20/16

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Multiple Solid Phases

196

Introduction to the Thermodynamics of Materials

Figure 7.13 The phase diagram for iron.

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11

The state d is that at which the extrapolated vapor pressure lines of the monoclinic and
the cubic lines meet in the phase field of stable tetragonal ZrO2. The state d is thus the
metastable triple point for the equilibrium between vapor, monoclinic, and cubic zirconia,
which occurs at a higher value of molar Gibbs free energy than that of tetragonal zirconia at the
same value of P and T. Similarly the state e, which is that at which the extrapolated vapor
pressures of tetragonal and liquid zirconia intersect in the phase field of stable cubic zirconia, is
the metastable triple point for equilibrium between liquid, vapor, and tetragonal zirconia.

P-T Diagram

Figure 7.15 A schematic phase diagram for zirconia, ZrO2.

10/20/16

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12

G-T Representation
Figure 7.13 The phase diagram for iron.

Figure 7.14 Schematic representation of the variation of the molar

Gibbs free energies of the bcc, fcc, liquid, and vapor

phases of iron with temperature at constant pressure.

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13

Phase Equilibrium in a One-Component System 199

The development of phase diagrams for one-component systems demonstrate the use of the
Gibbs free energy as a criterion for equilibrium when T and P are chosen as the independent variables.

Numerical Example

7.9 NUMERICAL EXAMPLES

Example 1

The vapor pressure of solid NaF varies with temperature as

and the vapor pressure of liquid NaF varies with temperature as

Calculate:
a. The normal boiling temperature of NaF
b. The temperature and pressure at the triple point
c. The molar heat of evaporation of NaF at its normal boiling temperature
d. The molar heat of melting of NaF at the triple point
e. The difference between the constant-pressure molar heat capacities of liquid and solid
NaF
The phase diagram is shown schematically in Fig. 7.16.
(a) The normal boiling temperature, Tb, is defined as that temperature at which the
10/20/16

saturated vapor pressure of the liquid

1 atm.
MSEis513
Xu Thus from the equation for the vapor
pressure of the liquid, Tb, is

14

Calculate:
a. The normal boiling temperature of NaF
b. The temperature and pressure at the triple point
c. The molar heat of evaporation of NaF at its normal boiling temperature
d. The molar heat of melting of NaF at the triple point
e. The difference between the constant-pressure molar heat capacities of liquid and solid
NaF

Example- (a) Part

The phase diagram is shown schematically in Fig. 7.16.

(a) The normal boiling temperature, Tb, is defined as that temperature at which the
saturated vapor pressure of the liquid is 1 atm. Thus from the equation for the vapor
pressure of the liquid, Tb, is

which has the solution

(b) The saturated vapor pressures for the solid and liquid phases intersect at the triple
point. Thus at the temperature, Ttp, of the triple point

10/20/16

MSE 513 Xu

15

Example- (b) Part

which has the solution

(b) The saturated vapor pressures for the solid and liquid phases intersect at the triple
point. Thus at the temperature, Ttp, of the triple point

200 Introduction to the Thermodynamics of Materials

which has the solution
Figure 7.16 Schematic phase diagram for a one-component system.

The triple-point pressure is then calculated from the equation for the vapor pressure
of the solid as

or from the equation for the vapor pressure for the liquid as
10/20/16

MSE 513 Xu

16

Example- (c) Part

Phase Equilibrium in a One-Component System

201

(c) For vapor in equilibrium with the liquid,

Thus

and, at the normal boiling temperature of 2006 K

(d) For vapor in equilibrium with the solid

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MSE 513 Xu

17

Example- (d) Part

and, at the normal boiling temperature of 2006 K

(d) For vapor in equilibrium with the solid

Thus

At any temperature

and thus

202

Introduction to the Thermodynamics of Materials

At the triple point

(e) H(sl)=27,900+4.24T:

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MSE 513 Xu

18

Example- (e) Part

202

Introduction to the Thermodynamics of Materials

At the triple point

(e) H(sl)=27,900+4.24T:

Example 2

Carbon has three allotropes: graphite, diamond, and a metallic form called
Graphite is the stable form of 298 K and 1 atm pressure, and increasing the pr
graphite at temperatures less than 1440 K causes the transformation of graphite to
and then the transformation of diamond to solid III. Calculate the pressure whi
applied to graphite at 298 K, causes the transformation of graphite to diamo
10/20/16

H298 K, (graphite) H298 K, (diamond)

= Xu
1900 J
MSE 513

19

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10/20/16

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Numerical Example

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uj

ppAd:\ u YA bA_\dQ !d: )g\_\dQ pg\d !A _!)A_A:  !d:  \d \QA ueu

Y!A :\!Q!b
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10/20/16

MSE 513 Xu

21

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Numerical Example-cont.


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Y!A :\!Q!b Jg \_\2gdu YA pA\dAd pgpA\A gJ pA \_\2gd !A Q\Ad \d

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h B 
pAb\ 2gbp!\gd gJ YA 2gAJK2\Ad8
7

h  A

P

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h Sj !b7 v ABqPSBJjOtB7 h jJO t j !b

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YA !pg pAA 2A \ Q\Ad )7

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pg\d7
} *

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w

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10/20/16YA \p_A pg\d S q  7 !_g _\A gd YAMSE
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gQAYA \Y YA
YA! gJ )_\b!\gd8 \dg z!\gd uO g A!_!A YA 2gAJK2\Ad8
7

22

 pY!A8 !d: Y! Jg YA  pY!A8 2g\d2\:Au

Y\ \__ dg )A A gJ gbA pgpA gYA Y!d  g  \ A: \d YA :A2\p\gd
gJ YA !A gJ YA g pY!Au ppgA YA pgpA\A gJ YA p!\2\p!\dQ pY!A !A
:A2\)A: \d Ab gJ YA\ pAA8 q !d: bg_! g_bA8 q \uAu8 ppgA YA
:\!Q!b \ p_gA: \d Sq 7 p!2Au Y\_A YA 2gd:\\gd Jg Az\_\)\b Az\A YA
pAA g )A YA !bA \d )gY pY!A8 YA bg_! g_bA8   !d:   \__ dg8 \d
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!ppA!!d2A Jgb YA \bp_A Sq 7 p_g8 \QA ujju

Alternative Representation


-

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6
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  ujj
_Ad!A 2gd2\gd Jg d! pY!A :\!Q!b 2gbp!A YA p_g \d r!s Sq 7
p!2A \Y YA :\!Q!b Jg YA !bA )!d2A \d Sq 7 p!2A r)s !d: Sq 7 p!2A r2su

10/20/16

MSE 513 Xu

23

Homework
Dehoff
7.3 7.4 7.7 7.11
Gaskell
7.8
Due date: Oct 27th

10/20/16

MSE 513 Xu

24