37

2.12 Gibbs Free Energy and the Thermodynannc Functions?

G = I 1- TS,

or G == (l + PV) - TS.

Differentiating, Since

dG = lill + PdV + VdP - TdS - SdT. dU = lIq - PdV,

(2.19)

(2.20)

and

dS:::;: dq for a reversible change, T

Eq.(2.19)

and can be written as dU =: liS - PdV. Substituting the value of dU in Eq.(2.19), dG = VdP - SdT.

(2.21 )

At constant pressure and variable temperature, (2.21) gives

(aG; ==-8 aT) ,

(2.22)

At constant temperature and variable pressure, (2.21) gives

(ac] = V

ap ,

(2.23 )

Similarly, for any reaction

( atJ.G ': =-tJ.S aT '/'

(2.24)

and

(2.25)

Eq. (2.24) suggests that the -lope of a plot of tJ.G against T gives the entropy change tJ.S with the opposite sign. Eqs.(2,_:-J.) and (2.25) are also valid for tJ.Go provided the other thermodynamic properties arc referred to the standard state. For example,

(2.26)

2.13 Gi bbs-Helmholtz Eq u ati on

tJ.G == tJ.H - T tJ.S.

Substituting Eq,(2.24) in the .ibove equation,

tJ.G == tJ.H + T( atJ.G \ aT r ,

This is known as the Gibbs- Helmholtz equation, and could also be written in the following

(2.27)

38

form:

[a(~G IT)]

aT "

(2.28)

or

[a(~GIT)] =~H a(l IT)

I'

(2.29)

The Gibbs-Helmholtz equation permits the calculation of ~Go for a reaction at any temperature from its value at another temperature. Similar equations can also be written for ~Go. For example,

(2.30)

(2.31)

The application of the Gibbs-Helmholtz equation is illustrated in Examples (2.J) and (2.K).

Example 2.J

Calculate the standard enthal i!Y and entropy changes at 25°C (298 K) for the reaction 2<Cu> + 112 (02) = < CU20>;

AGO = -40,500 - 3.92 T Jog T i- 29.5 T cal

(-169,452 - 16.40 T ]u':', T + 123.43 T J).

Solution: ~Go = -40.500 - : l)2 x 0.4343 TIn T + 29.5 T

= -40,500 - 1,702 T In T + 29.5 T, (2.1.I)

~Go = _ 40500 -I, 702lnT + 29.5

T T

Differentiating,

a(~GO IT) 40500 1.702

--,- __ ...,;_ = __ . - --

er T2 T

From Eq.(2.31),

~Ho 40500 1.7()2

---= - __ . --

I

or ~Ho = -40,500 + 1.7(l_:_l T

At 25°C,

~Ho = -40,500 + l.7(): x 298

= -39,993 cal= -:19.99 kcal Differentiating (2.1.1),

39

a/)"GO

-- = -1.702 -1.702ln T + 29.5 aT

= 27.798 - 1.7()2 Ln T.

From Eq.(2.26),

-/)"SO == 27.79R - 1.702 In T.

/)"S298 = -27.7l),'I, + 1.702 In 298 = -18.10 cal/deg.

Example 2.K.

/)"Go for the reaction <Ni> -,- ~ (02) = <NiO> at 25°C (298 K) is -50,786 cal (-212,489 J). Calculate /)"Go at 327°C (600 K) from the following data:

/)"Ho298<NiO> = -57,500 cal/mole (-240,580 J/mol)

Cp<Ni> = 6.03 + 10.44 x I 0-6'j2 - 2.50 x I 0·3T calldeglmole (25.23 + 43.68 x 10-61'2 - 10.46 X 10-3 T J/K/mol).

Cp(02) = 7.16 + 1.0 x 10-3T - ().4 x 105T2 calldeg/mole (29.96 + 4.184 x 10-" i - 1.67 x 105r2 J/K/mol).

Cp<NiO> = 12.91 cal/deg/rnole (54.0 I J/K/mol).

Solution: Applying the Gibbs-Helmholtz equation to the reaction under question, 6.Go = _f6.HO dT

T T2

or

(2.K.l )

But, 6.Ho = - f6.Cl'dT

6.Ho = - f(cl' < Nit)» - ('I'<Ni> -I 12CI'(U2)dT

= fI2.91- (6.03 + 1 OA4xl 0-6 T2 - 2.50x1O-J T) -112(7.16 + 1.0xlO-3 T - O.4xl 05 T-2 )dT = f3.30-10.44xIO+j'2 +2.0xlO-3T+0.2xI05T-2)dT

__ 3.10T _ 10.44xI0'" '.1 .. '_.1 + 2.0xI0-JT"

.J ---- -0.2xI05T-1 + 6.Ho

3 I

(2.K.2)

where 6.H is an integration constant. At 25°C, the standard enthalpy change of the reaction is - 57,500 callmole. Putting this value in (2.K.2),

-57500 = 3.30x298 10.44xlo-62983 + 2.0xI0-32982 -0.2xI05298-1 +/)"Ho'

3 2

40

= 913 + !lHo

or LlHo =-57,500-913=-)K,413. Putting the value of LlHo in (:2 .1<.2),

!lHO = 3.30 T - 3.48 x 1O-6T3 + 1.0 X 10-3 T2 - 0.2 x 105 rl-58,413 or LlHo/T2 = 3.30 rl - 3.48:\ 10-6 T + l.0 X 10-3 - 0.2 X 105 r3-58,413 rSubstituting the value of !lH(jrr2 in (2.K.1),

so: =-T f(3.30T-' -3.48xl0-6T+1.0xl0-' -0.2xl05T-3 -58413T-2)dT

!lGo =-T[3.30InT- J.48xl0-6 T2 +1.0xlO-JT+ 0.2xl05 T-2 + 58413T-, +1]

2 2 1

(2.K.3) !lGo = [-3.30T In T + 3.48xl 0-6 T3 -1.0xl 0-3T2 _ 0.2x105 T-' _ 58413 -IT] 221

(2.K.3)

where I is an integration constant. At 25°C, the standard free energy change of the reaction under question is -50,786 cal. Substituting this value in the above equation,

-50786 = -3.30x2981n298 +- 3.48xl0-6 2983 -1.0xl0-32982 _ 0.2xl05 298-1 _ 58413 -1298]

2 2 1

= - 64,091.85 - 298 I. 298 1=- 64,091.85 + 50,n6 = - 13,305.85,

or 1=- 44.65.

Putting the value ofI in (2.K.3),

!lCo =[-3.30TlnT-, .\~xl0-6 r-1-l.OxlO-'r2 _ 0.2x105 T-1 _ 58413 + 44.65T] 221

!lCo =[-58413+1.7-J.dO-6rJ -1.0xl0-'T2 -3.30TlnT+44.65T-O.lxl05r-']

!5.G6000 =[-58413+1.74xl0 ('6003 -1.0xl0-'6002 -3.306001n600+44.65600-0.1xl05600-1]

= -44.290 cal.

41

Exercises

2.1 The reversible transformation of grey tin to white tin occurs at 13°C (286 K) and 1 atm,

and the heat of transformation is 500 callmo 1 e (2092 J/mol). Calculate the entropy change.

2.2 Calculate the changes in heat content and entropy associated with the reduction of the

oxides of iron and aluminium at 25°C, according to the following reactions:

Fe203 + 3C = 2Fe + J(,O. AI203 + 3C = 2Al + .1CO.

Comment on the result.

2Fe + 3/2 02 = Fe203

~H0298 = -200.000 cal (-836,800 J). 2A 1 +3/2 02 :_: A1203;

~H0298 = -404,000 cal (-1,690,336 J) C(graphite) + Y2 02 = CO;

~H0298 = -25,000 cal (-104,600 J).

Entropies of CO, AI, Fe, Ah03, Fe203 and C (graphite) at 25°C are 47.3, 6.7, 6.5,12.8,21.5,

Given:

and 1.39 cal/deg/mole (197.9,28.0,27.2,53.6,89.9, and 5.8 J/K/mol), respectively.

2.3 The heat capacity of sol id magnesium at 1 atm pressure in the temperature range from 0°

to 560°C (273 to 833 K) is gi veri by the expression

Cp = 6.20 + 1.33 x 10-3 T + ().78 x 104 r2 cal/deglmole (25.94 + 5.56 x 10-3 T + 28.37 x 104r2 J/K/mol).

Determine the increase of entropy per mole for an increase of temperature from 27° to 527°C (300 to 800 K.) at 1 atm (1 OJ J25 N/m2) pressure.

2.4 Two identical copper ingots, one at 500°C (773 K) and the other at 300°C (573 K) are placed in an insulated enclosure. Heat flows from the hot ingot to the cold ingot until the temperature of both ingots is the same (400°C). Calculate the total entropy change accompanying this process, assuming that the transfer of heat from the ingots to the material of construction of the enclosure is negligible. Comment on whether the process is spontaneous or not.

Given:

C, <ell> == 5.41 + ISO x 1O-3T cal/deglmole (22.64 + 6.38 x 10-3 T J/K/mol).

2.5 Calculate the standard entropy change of the following reaction at 727°C (1000 K) 2A1 + 3/2 02 = AhO:;;

42

.1S0298 = -74.87 cal/dcg/mole (-313.26 J/K/mol).

Given: Melting point of aluminium = 659°C (932 K).

Heat of fusion of Al at the m. p, = 2,500 cal Imole (10,460 J/mol). c, <Ah03> = 25.14 cal/deg/mole (105.19 J/K/mol).

c, (02) = 7.57 cal/deg/mole (31.67 J/K/mol).

Cp<AI> = 6.76 cal/deg/mole (28.28 J/K/mol).

Cp{AI} = 7.00 cal/deg/mole (29.29 J/K/mol)

2.6. Calculate the entropy change of the system and the surroundings for the isothermal freezing of one mole of supercooled liquid copper at 900 C (1,173 K.) when the surroundings are also at the same temperature. Assume that Cp for liquid copper also holds good for supercooled liquid copper.

Given: Melting point of copper = 1 ,083°C (1,356 K).

Heat of fusion of copper at m.p. = 3,100 cal/mole (12,970 J/mol).

Cp <Cu> = 5.41 + 1.50 x 1O.3r cal/deglmole (22.64 + 6.28 x 10.3 T J/K/mol). Cp{Cu}= 7.50 cal/deg/mole (31.38 J/K/mol).

2.7. Calculate the entropy changes of the system and surroundings for the case of isothermal freezing of one mole of supercooled liquid silver at 850°C, when the surroundings are also at the same temperature.

Given: Melting point of silver = 961°C (1234 K).

Heat of fusion of silver at 961 '"C = 2,690 cal/mole (11,255 J/mol).

Cp <Ag> = 5.09 + 2.04 x 1 U-3 T cal/deglmole (21.30+ 8.54xI0·3 T J/K/mol). Cp, {Ag} = 7.30 cal/deg/rnolc (30.54 J/K/mol).

2.8 Using the following values, calculate the standard free energy change per mole of the

metal at 727°C (1,000 K) for the reduction of molybdic oxide and chromic oxide by hydrogen: ~GoIOOO<Cr203> = -205.5 cal/mole (-859.8 k.I/rnol).

~GoIOOO<Mo03> = -120.0 kcal/rnole (-502.0 kJ/mol).

~GoIOOO(H20)= - 45.5 kcal/rnolc (-190.4 kJ/mol).

Comment on your result.

2.9. Determine the temperature above or below which reduction of MnO by carbon becomes thermodynamically feasible <It 1 atm pressure (101,325 N/m ).

Gi ven: 2<C> + (02) = 2 l CO);

43

flO° = -53,400 - 41.9 T cal (-:223,426 - 175.3T J). 2<Mn> + (02) = 2<MnO>;

flO° = -190,800 + 39.25 T cal (-798,207 + 164.2 T J).

2.10. The standard heat of formation of solid HgO at 25°C (298 K) is -21.56 kcallmole (- 90.20 kJ/mol). The standard entropies of solid HgO, liquid Hg, and O2 at 25°C are 17.5, 18.5, and 49.0 calldeg/mole (73.22, 77.40 and 205.01 J/K/mol), respectively. Assuming that ~Ho and flSo are independent of tern perature, calculate the temperature at which solid HgO will dissociate into liquid Hg and 02.

2.11 There are two allotropic forms of tin - grey and white. The enthalpy change at 25°C

(298 K) for the reaction

Sn (grey) --> Sn (white)

is 0.5 kcal (2.09 kJ). The entropy change is 1.745 calldeg (7.30 J/K). Using the free energy criterion for equilibrium, and assuming ~Ho and ~So to be independent of temperature, calculate the transition temperature, i.e. the temperature at which grey and white tin co-exist in equilibrium.

2.12. Determine the tempera lure above or below which the reduction of MgO by Al becomes thermodynamically feasible LIt 1 atm pressure (101,326 N/m ).

Given: 2{Al) + 3/2 (02) = <AI203>;

~Go=-401,500+76.91 T (Mg) + ~ (02) = <Mg(»;

.60° = - 401,500 + 76.91 T cal (-1,679,876 + 321.79 T J) . .60° = -174,750 + 49.09 T c~t! (-731,154 + 205.39 T J).

2.13. Chromium and carbon present in stainless steel form chromium carbide at 600°C (873 K). Show by thermodynamic calculation which of the metals among Si, Ti, and V should be alloyed to stainless steel, so as to prevent the formation of chromium carbide.

Given: 3 Cr + 2C = Cr3C_:;

~Go = -20,800 - 4.0 '] cal (-87,027 - 16.74 T J). Si + C = SiC;

~Oo = -12,770 +1.66 T cal (- 53,430 + 6.95 TJ). V +C =VC;

~Oo = -20,000 + 1.6 T cal (-83,680 + 6.69 T J).

44

Ti + C =TiC;

~Go = -45,000 + 2.8 T cal (-188,280 + 11.71 TJ).

2.14. Suggest whether the decomposition of NbC by Nb203, at 1 atm pressure is possible at 1500°C (1773 K).

Given: ~Go1773 <Nb205> = -269.0 kcallmole (-1,125.5 kJ/mol).

~Go1773 <NbC> = -30.8 kcal/mole (-128.87 kJ/mol). ~GoI173(CO) = -64.0 hal Imole (-267.77 kJ/mol).

2.15. Determine which of the following metals can be produced by the reduction of metal sulphide with metal oxide at I OOO°C (1273 K) and 1 atm pressure (101,325 N/m2).

Given: CU2S + 2CU20 = 6Cu + S02;

~Go = 28,530 + 14.06 T log T - 70.43 T cal (119,570 + 58.83 T log T - 294.68 T J).

PbS + 2PbO = 3Pb + S02;

~Go = 98,440 + 16.1 T log T - 121.14 T cal (411,873 + 67.36 T log T - 506.85 T J).

Ni3S2 + 4NiO = 7Ni -I- 2S02;

~Go = 139,800 - 98.59 T cal (584,923 - 412.5 T J).

2.16. Is the reaction <Fe20;> + 3(H2) = 2<Fe> + 3(H20) spontaneous at 25°C (298 K) and 1 atm pressure (101,325 N/m2)?

Given: ~Ho298,(H20) = -57,1'69 callmole (-241,789 J/mol). ~Ho298,(Fe203) = -196,500 callmole (-822,156 J/mol). S0298,(H20) = 45.10 cal.deg/rnole (188.7 J/K/mol), S0298,<Fe> = 6.49 cal/dcg/mole (27.1S J/K/mol). S0298,(H2) = 31.21 cal/deg/rnole (130.58 J/K/mol). S0298,<Fe203> = 21.50 cal/deg/mole (89.95 J/K/mol).

45

CHAPTER 3

THE CLAUSIUS-CLAPEYRON EQUATION

3.1 Introduction

The Clausius-Clapeyron equation is of great importance for calculating the effect of change of pressure (p) on the equilibrium transformation temperature (T) of a pure substance, and may be represented as

dp

=

dT J'6.V

/l:.H

(3-1)

where 6.H is the heat of transformation and 6. V is the volume change associated with the transformation. However, care should be taken in selecting the units of the quantities in Eq.(3.1). If 6.H and 6. V are expressed in cal and cubic centimeter respectively, then the value of dp/dT obtained will be in cal/c.c./deg. In order to convert the value of dp/dT from this unit to the more convenient unit of atm/deg, the following factor is used:

1 cal = 41.293 c.c. atm.

3.2 Application of Clausius-Clapeyron Equation to Phase Changes

The Clausius-Clapeyron equation is applicable to any phase change-fusion, vaporization, sublimation, allotropic transformation, etc.

3.2.1 Liquid-Vapour (Vaporization)

Equilibria Applying Eq.(3.1) to a liquid-vapour equilibrium, we have

dp 6.Hv

=---'----

dT T (Vvop - VI,III )

(3.2)

where t;..I-Iv is the molar heal of vaporization or latent heat of evaporation, VVap is the molar volume of vapour, and Vjiq is the molar volume of liquid. Since the molar volume of vapour is very much larger than the molar volume of liquid, Vjiq is negligible as compared to V yap and hence

dp 6.Hv

-=--

dT rr.;

Assuming that the vapour behaves as an ideal gas, the volume V yap may be related to

(3.3)

RT

Vvap = - (3.4)

P

Substituting the value of V in Eq.(3.3),

46

dp ptlHv

=

dT

(3.5)

The equation can be rearranged in the most generally used differential form

d(lnp) ,1H"

--'-~-'- =

dT RT2

(3-6)

If we assume as an approximation, however, that over the interval in question tlHv remains

constant, then integration of Eq.(3.6) yields

I tlHv C I np=---+ '

RT

(3.7a)

or

log p = _ tlH v + (' 2.303RT

(3.7b)

where C' and C are integration constants.

It is evident from Eq.(3.7b) that if log p for any liquid metal is plotted against liT, the plot should be a straight line. The slope (m) of the straight line will be given by

tlHv

m=

2.303R

and the intercept of the line with Y-axis will give the value of constant C. From the slope of line, the heat of vaporization of liquid may be calculated. However, the heat of vaporization of a liquid metal calculated in this way will be the mean value over the temperature interval concerned.

Eq.(3.6) may also be integrated between the limits PI and P2 corresponding to temperatures TI and T2 respectively. Assuming that the temperature range is small enough so that tlH is independent of temperature, integration of Eq.(3.6) yields

p2 tV{ T2dT

Jd(lnp) = _v J--:;-

pi R TI 7 .

or

(3.8)

Eq.(3.8) may be used to calculate the vapour pressure at any temperature if the vapour pressure at another temperature and the mean heat of vaporization over that temperature range are known.

The following example illustrates the application of the Clausius-Clapeyron equation to liquid-vapour equilibria.

Example 3. A The vapour pressure of liquid titanium at 2227°C (2500 K) is 1.503 mm Hg (200 N/m ). The heat of vaporization at the normal boiling point of titanium is 104 kcallmole

47

(435.14 kllmol). Calculate its normal boiling point.

Solution: Let us assume that the normal boiling point of titanium is Tb. At this temperature, the vapour pressure is equal to 1 atm, or 760 mm Hg. Putting the appropriate values in Eq.(3.8),

10 760 _ -104000 (_1 __ 1_) g 1503 - 2.303(1.987) T, 2500

On simplification,

T. = 3558 K = 3285°C.

Thus the normal boiling point of titanium is 3285°C.

However, a more accurate integration of Eq.(3.6) can be carried out if the variation of heat of vaporization with temperature is taken into account. Using Kirchhoff's equation at constant

pressure,

(dLlHv) = LlC

dT p

LlH v = fLlCpdT + 11

(3.9)

where I" is an integration constant. Putting the value of LlH in Eq. (3.6)

d(ln p) f LlC pdT 11

----'-----'--'- = + ---

dT RT2 RT2

(3.10)

On integration,

I f dT f C' tr 11 1

n p = --? Ll I'C j - --? + 2

RT- RT-

(3.1 1 )

where h, is another integration constant. If Cp is independent of temperature, Eq.(3.11) reduces to

t1C P 11

Inp = --lnT--- + 1

R R7 2

(3.12)

3.2.2 Solid-Vapour (Sublimation) Equilibria

On the basis of assumptions similar to those made in liquid-vapour equilibria, an expression similar to Eq.(3.6) may also lx> obtained for solid-vapour equilibria.

d (In p) = t1H\. (3 .13 )

dT RT2

where t1Hs is the heat of sublimation.

48

3.2.3 Solid-Liquid (Fusion) Equilibria

Applying the Ctausius-Clapeyron equation to solid-liquid equilibria,

dp .1Hj
-=
dT T(~,q - V",/Id)
dT T(~", - V",/Ui )
or -=
dp .1Hj (3.14)

(3.15)

where ilH, is the molar heat of fusion, Vliq and Vsolid are the molar volumes of liquid and solid respectively.

Eq.(3.15) may be applied to calculate the change in melting point of a metal with change of pressure, as illustrated in the following example.

Example 3.B

The melting point of gallium is 30°C (303 K) at 1 atm (l 0 1 ,325 N/m2). The densities of solid and liquid gallium are 5.gS5 and 6.08 g/c.c. (5.885 x 103 kg/m ' and 6.08xlO kg/m:') respectively. The heat of fusion of gallium is 18.5 cal/g, (77.40 x 103 J/kg). Calculate the change in melting point of gallium for an increase of pressure of 1 atm (l 0 1 ,325 N/m2). Solution: Molar volume of liquid gallium, VJiq

Atomic wt of gallium x

= =--cc

Density of liquid gallium 6.08

where x denote the atomic weight of gallium.

Similarly, molar volume of solid gallium, Vsolid = _x_cc 5.885

The value of heat of fusion of gallium is given in cal/g. In order to find the value in terms of cal/mole, we must multiply b) its atomic weight. Thus,

Molar heat of fusion == 18.5 x callmole.

Putting the appropriate values in Eq.(3.14),

dp

-=---..,....---

dT

18.5x --cal I C.c / deg

(X ..

303 6.08 - -5.~g5

In order to change the value ill atm/deg, we should use the conversion 1 cal = 41.293 c.c. atm.

Thus,

49

dp 18.5x41.293 /d

-= atm eg

dT 303( 6.~8 - 5:~85-)

=-462.7 atrn/deg.

For

dp = -2.6xl 0-3 degl atm dT

dP = I atrn,

dT = -2.16 x 10-3 deg,

Thus, the melting point of gallium will be decreased by 2.16 x 1O-3deg.

or

3.2.4 Solid-Solid Equilibria

The rate of change of transition temperature at which two crystalline forms of a solid are in equilibrium with pressure is given by an equation similar to that discussed earlier. If a is the stable form above the transition temperature, and ~ is the stable form below the transition temperature T, then accordin g to Eq. (3.1 ),

dp .6.H,r
= T(Va - VfJ)
dT
dT T(Va - VfJ)
or -=
dp .6.Htr where ,1Htr, is the molar heat of transition, Va and V p are the molar volumes of the indicated forms, all measured at temperature T.

3.3 Trouton's Rule

Trouton's rule states that the ratio of latent heat of evaporation to the temperature of normal boiling Ti is constant lor all liquids, and is approximately 21 cal/deg/mole, i.e.

,1Hv

-- = 2 leal / deg/ mole

~)

The rule is only an approximate one, and is not followed by all liquid metals. However, this rule may be used to derive an approximate value for latent heat of evaporation.

Example 3. C

The normal boiling point or zinc is 907°C (1180 K). Calculate its vapour pressure at 8000e (1072 K), assuming that zinc lollows Trouton's rule.

50

Solution: According to Eq .(3. 7b). the vapour pressure ofliquid zinc may be expressed as -M-f logp = 2.303~·T + C

(3.C.1)

Since zinc follows Trouton's rule, the molar heat of vaporization is given by

.6.Hv = 21 Tb,

= 21 x 1180

= 24.780 callmole.

Substituting the value of AI-I in Eq.(3.C.1),

I - 24,780 C

ogp - 2.303x1.98TJ-:' +

(3.C.2)

The value of C can be obtained by putting boundary conditions. The vapour pressure at the normal boiling point 907°C (I 180 K) is 1 atm, and hence we have

1 - 24,780 C

ogp = . +

2.303x1. 987x1 180

or C == 4.59.

Substituting the value of C in Eq.(3.C.2),

10 = - 24,780 + 4.59

gp 2.303x1.987T

(4.C.3)

where PIs in atm.

From Eq.(3.C.3), the vapour pressure of liquid at 800°C (1073 K) is given as

I - 24,780 459

ogp = + .

2.303xl.987 xl 073

= -0.4580.

or P = 0.3483 atm

= 264.7 mm Hg.

Thus, the vapour pressure of zinc at 800°C is 264.7 mm Hg.

51

Exercises

3.1 Calculate the mean heal of vaporization of palladium from the following vapour pressure data:

Temp.i X'

1314

1351

1568

V.P.,mmHg. 7.516 x 10-7 1.614 X 10-6 5.625 X 10-5

3.2 The vapour pressures of liquid thorium tetraiodide at 800°c (1073 K) and 825°C (1098 K) are 468 mm Hg (62,395 N/m2) and 660 mm Hg (87,993 N/m2) respectively. Calculate its mean heat of vaporization.

3.3 The heat of evaporation of copper at its normal boiling point is 74.5 kcallmo1e (311.71 kllmol). The vapour pressure of copper at 1500°C (1773 K) is 0.256 mm Hg (34 N/m2). Calculate the boiling point of copper.

3.4 The vapour pressure of I iquid zinc as a function oftemperature is given as

6,620

logptrnm.Hg) = _-- -1.25510gT + 12.34 T

Calculate the heat of vaporization of zinc at its boiling point 907°C (1180 K).

3.5 The densities of liquid and solid bismuth are 10.0 g/c.c. (lOx 103 kg/rrr') and 9.673 g/c.c. (9.673x103 kg/rn ') respectively at the normal melting point 270°C (543 K). The heat of fusion is 2.633 kcallmole (11.02 k.l/mol), Calculate the melting point of bismuth under a pressure of 100 atm (101,325 x102 N/m). Atomic weight of bismuth is 209.

3.6 The melting point of cadmium at 1 atm (101,325 N/m2) is 321°C (594 K) and its heat of fusion is 13.66 cal/g (57.15:d03J/kg). The volume change on the melting of cadmium is +0.0064 c.c./g (+0.0064xlO-\ m3/kg). Calculate the melting point of cadmium, (a) at 2 atm (202,650 N/m2) pressure, and (b) in vacuo.

3.7 Mercury melts at -38.87uC (234.13 K) at 1 atm (101,325 N/n/) pressure. The densities of liquid and solid mercury are 13.69 g/c.c. (13.69x10J kg/nr') and 14.19 g/c.c. (l4.19x103 kg/rn) respectively at the normal melting point. The heat of fusion of mercury is 2.33 callg (9.75x103 l/kg). Calculate the change ill melting point of mercury per atmosphere change in pressure.

3.8 The vapour pressure, P, (measured in mm Hg) of liquid arsenic, is given

52

by

2,460

logp = --- + 6.69 T

and that of solid arsenic by

6,947

logp = --- + 10.8

T

Calculate the temperature at which the two forms of arsenic will have the same vapour

pressure.

3.9 The densities of ice and liquid water at 1 atm (202,325N/m2) and O°C (273 K) are 0.917 g/c.c. (0.917x 1 03 kg/m3) and 0.9998 g/c.c. (0.9998 x w3 J/kg) respectively. The heat of fusion of water is 80 callg (334.72x 103J/kg). Calculate the melting point of ice at 0.5 atrn (50,682.5 N/m2) and 101 atm (102,338 X 102 N/m2).

3.10 The heat of the reaction Sn (grey) = Sn (white) is 500 callmole (2,092 J/mot) at the transition temperature of 13 °C (286 K). The atomic weight of tin is 118.7 and the densities of grey and white tin are 5.75 g/c.c. (5.75x103kg/m3) and 7.28 g/c.c. (7.28xI03 kg/rrr') respectively.

Calculate the change in the transition temperature if the pressure on the grey tin phase is increased by 100 atm (101,325x102N/m2).

3.11 Liquid mercury boils at 35?OC (630 K) at 1 atm (101,325 N/m2). Calculate its

approximate vapour pressure at 100°C (373 K), assuming that it follows Trouton's rule.

53

CHAPTER 4

FUGACITY, ACTIVITY AND EQUILIBRIUM CONSTANT

4.1 Fugacity

The combined statement of the first and second laws of thermodynamics for a system doing work against pressure is

dG = VdP - Sd'T.

(4.1 )

At constant temperature, Eq.(5.1) reduces to

dG=V dP

( 4.2)

For one mole of an ideal gas. Eq.( 4.2) reduces to dG = RT din P.

If the gas is not ideal, Eq.(4.3) takes the form

dG=RTd In r. (4.4)

where the function f is called 'fugacity' of the gas. For an ideal gas, the fugacity is numerically equal to the pressure at all pressures. Non-ideal (or real) gases approach ideal behaviour as the pressure is decreased, i.e. as P ~ 0, f ~ P. Thus, for a non-ideal gas, fugacity and pressure will be numerically equal at low pressures. Fugacity can be regarded as an idealised measure of the pressure of a gas.

4.2 Activity

The activity of a substance may be defined as the ratio of fugactiy of the substance to its fugacity in its standard state. Mathematically,

(4.5)

where a is the activity, f is the fugacity in any arbitrary state, and f? is the fugacity in the standard state. Putting the value of fugacity from Eq.(4.5) in Eq.(4.4),

dG = RT din (f".a).

Since f:U is constant at constant temperature,

dG = RTd In a.

(4.6)

Integrating the above equation from the standard state to any arbitrary state, G - GO = RT In a - RT In a",

where a? is the activity at the standard state. Since a? is unity,

G-Go=RTlna. (4.7)

A more detailed treatment of activity will be given in the chapters dealing with solutions.

54

4.3 Equilibrium Constant

Consider a chemical reaction

aA + bB + ... = rR + sS + ... (4.8)

at constant pressure and temperature, where A, B, .... are reactants, R, S .. are products, and prefixes are the number of g-atoms or g-molecules of the corresponding species.

The free energy change of reaction (4.8) may be written as

.6.G = 2:0 product - I () reactant

= (rOR+ sOs -1- .••• ) - (aOA + bOB + .... ). (4.9)

If the reactants and products are present in their standard states, then the free energy change, .6.0°, may be written as

.6.0 = (rOOR + soos -r- ..• ) - (aO° A + bOOB + .... ) Subtracting the above two eq uations,

.6.0 -.6.GO = [r(GR - GOR) + s(Gs - GOs)+ .... ] -[a(OA - 0° A) + beGs - OOB)+ .... ].

(4.10)

Substituting the values of (0 - 0°) from Eq.( 4.7) .

.6.0 _.6.0° = [r(RTlnaR) + s(RTlnas)+ .... ] -[a(RTlnaA) + b(RTlnaB)+ .... ].

or

(5-11)

If the reactants and products are in equilibrium with each other, the free energy change ag is zero, and hence

r,

o a «a "

.6..G = -RT In--·-·

aClAa"l!

r s

The term In a /la/s is called the thermodynamic equilibrium constant or 'equilibrium

aClAa'H .

constant', and is denoted by K. Hence, at equilibrium,

.6.GO = -RT In K.

(4.12)

In the case of traditional units, .6.0° is expressed 111 cal, and the value of R is 1.987 calldeg/mole. Putting the val LIe of R and changing to common logarithm, Eq.( 4.12) becomes

.6.0° = -4.575 T log K.

(4.13)

In the case of SI units, .6.0° is expressed in Joules, and the value of R is 8.314 JIKlmoi. The equivalent of Eq.( 4.13) in the Sl units is

.6.0° = -19.147 T log K.

It is evident from Eq.( 4.12) that the equilibrium constant of a reaction can be calculated from

55

knowledge of the standard free energy change of the reaction.

The application of equilibri urn constant in predicting the stability of a specified oxide refractory under a designated atmosphere has been illustrated in Example 4A. Example 4.B illustrates how the value of the equilibrium constant helps in deciding the suitability of a gas mixture for the bright annealing of a metal sheet in heat-treatment practice, while calculation of the equilibrium composition of a gas mixture has been illustrated in Example 4.C.

Example 4. A

Calculate the equilibrium constant and equilibrium partial pressure of oxygen for the reaction Zr02 = Zr + O2 ;

.6.0° == 259.940 +4.33 T log T - 59.12 T cal

(l ,087,589 + 18.12 T log T - 247.36 T J),

at 1727°C (2000 K). Also, predict the possibility of decomposing a pure zirconia crucible under a vacuum of 10-5 mm Hg (123 x 10-5 N/m2) at that temperature.

Solution: The standard free energy change for the reaction

Zr02 = Zr + O2 (4.A.1)

at 1727°C (2000 K) is given by

.6.0°2000 = 259,940 + 4.33 x 2000 x log 2000 - 59.12 x 2000 = 170.330 cal.

The equilibrium constant of reaction (4.A.1) can be calculated with the help of Eq.(4.l3), and thus the value of K at 1727°C is given by

10 K = _ 170330

g 1.9g7x2.303x2000

=-18.61.

Taking antilogs,

K = 2.455 X 10-19

The equilibrium constant of reaction (4.A.1) is

K = aZram a Zr()2

where azr, a02, and aZr02 are the activities of Zr , O2 and Zr02, respectively. Assuming that the gases behave ideally, the activity of oxygen may be replaced by its partial pressure, i.e.

K = aZrPm a Zr(}2

where po2 is the partial pressure of oxygen in equilibrium with Zr and Zr02. Pressure in the expression for K is in fact a ratio of the partial pressure of the gas (expressed in atm) to the standard pressure, i.e. 1 atm. and hence has no units. The magnitude of the pressure term in the

56

expression for K is, therefore, equal to the partial pressure of the gas expressed in atm.

Since both Zr and Zro2, are pure, and hence their activities may be taken as unity, it follows that

K=P02 Putting the value of Kin Eq.(4.A.2),

P02 = 2.455 x10-1l) atm

= 760 x 2.455 x 10-19 mm Hg = 1.865 X 10-16 mm Hg.

(4.A.2)

Thus, the partial pressure of oxygen in equilibrium with Zr and Zr02 at 1727°C is 1.865x 10-16 mm Hg. In other words, if the partial pressure of oxygen in the system is below this value at 1727°C, then zirconia will decompose. In the present problem, the vacuum is of the order of 10-5 mm Hg, which is equivalent to a partial pressure of oxygen of 0.21 x 10-5 mm Hg assuming that air contains 21 % oxygen on volume basis), and this value is greater than the equilibrium partial pressure of oxygen in contact with Zr and Zr02 at 1727°C. Hence, there is no possibility of the decomposition of zirconia crucible.

Example 4.B

Calculate the equilibrium constant for the reaction

<NiO> + (H2) = <Ni> + (H20) at 750°C (1,023 K) from the following data: <Ni> + Y2 (02) = <NiO> ; ilGo = -58,450 + 23.55 T cal

(-244,555 + 98.53T J) .

(H2) + 1;2 (02) = (H20)~ ilGo = -58,900 + 13.1 T cal

(-246,438 + 54.81 T J).

Could pure nickel sheet be annealed at 750°C (1,023 K) in an atmosphere containing 95% H20 and 5% H2 by volume without oxidation?

Solution: (H2) + 1;2 (02) = (H20); ilGo = -58,900 + 13.1 T cal <Ni> + 1;2 (02) = <NiO>; ilGo =: -58,450 + 23.55 T cal On subtraction,

<NiO> + (H2) = <Ni> + (I-hO); ilGo = -450-10.45T cal.

At 750°C (1023 K),

ilGo1023,(4Bl) = - 450 - 10.45xl023 = -I L: 40 cal.

From Eq.(4.13) it follows that ilGo logK=---- 4,575T

(4.B.1)

57

Putting the appropriate values in the above equation,

10gK=- 11,140 =2.38

4.575x102J

Taking antilogs,

K == 240

and aNiO and aNi are unity,

K = PH20 PH2

(4.B.2)

Putting the value of Kin Eq.(4.B.2),

K = PH20 = 240.

PH2

Thus, the equilibrium P H2() ratio for reaction (4.B.1) at 750°C is 240.

PH2

Now consider an enclosed system in which nickel and nickel oxide are kept at 750°C in a H2-

H20 atmosphere. If the PI120 ratio of the atmosphere is less than the equilibrium value

PH2

calculated above, then the forward reaction will occur, i.e. nickel oxide will be reduced to Ni

~d H20, until the P H2O ratio equals the equilibrium value. Conversely, if the P H2O ratio is

Pin PH2

greater than the equilibrium value, the backward reaction will occur, i.e. nickel will oxidise

until the equilibrium P H2O value is reached.

PH2

Alternatively, suppose a constant P H2O value is maintained (as in, the present example) by PH2

passing a rapid stream of H2- I-bO gas mixture of constant composition over the nickel and

nickel oxide at 750°C. If the P/lW ratio of the gas mixture is less than the equilibrium value, PN2

the reaction will proceed to the right, i.e. nickel oxide will be reduced to nickel. But in doing

so, the P H2O ratio of the gas stream is not significantly changed and the stable state will be PN2

pure nickel. In a similar way, if the PfI2() ratio is greater than the equilibrium value, the PH2

reaction win proceed to the left, i.e. nickel will be oxidised, and thus the stable state is nickel oxide. In the present example, the gas atmosphere contains 95% H20 and 5% I-b, i.e. the

58

P H2O ratio is 19, which is less than the equilibrium value of 240 at 750°C, and thus PH2

reduction of NiO will take place. Hence, if a nickel sheet is heated in the given atmosphere at 750°C, it can be annealed without oxidation. Additionally, any oxide layer present on the sheet surface will be reduced.

Example 4. C A gas mixture of the following composition by volume:

CO: 30%, CO2: 10%, H2: 10%, and N2: 50%

is fed into a heat-treating furnace at 927 C (1200 K). Calculate the equilibrium composition of the gas mixture, assuming the total pressure in the furnace to be 1 atm (101,325 N 1m2), from the following data:

<C> + ~ O2 = (CO): t,GO = -26,700 - 21.0 T cal (-111,713 - 87.86 T J).

<C> + (02) = (C02); t,GO = -94,200 - 0.2 T cal (-394,132 - 0.841 J).

(H2)+1I2 (02) = H20; i3.Go = -58,900 + 13.0 T cal (-246,438 + 54.39 T J).

Assume that all the gases behave ideally.

Solution: When the gas mixture containing CO, CO2, and H2 (N2 being inert) is fed to the furnace, the gases will tend to react with each other until equilibrium is established for the reaction

(4.C.I)

Hence, the composition of the gas mixture at equilibrium will be somewhat different from the original. As is evident from reaction (4.C.l), H20 will also be present at the equilibrium. Thus, the problem reduces to one of finding the standard free energy change of reaction (4.C.1) and calculating the value of the equilibrium constant. Since the equilibrium constant is related to the partial pressures of the gases, the equilibrium composition of the gas mixture can be calculated.

(4.C.2)

<C> + Y2 (02) = (CO) (4.C.3)

(H2) + Y2 (02) = H20 (4.CA)

(4.C.2)-(4.C.3)-(4.CA) gives the required reaction

(CO) + (H20) = (C()~) + (H2), (4.C.5)

and the free energy change is given by

t,GO = (-94,200 - 0.2 T) - (-26,700 - 21.0 T) - (-58,900 + 13.0 T)

= -8,600 + 7.8'1' cal. (5.C.6)

The free energy change of reaction (5.C.5) at 927°C (1200 K) is

59

.6.0° = -8.600.7.8x 1200 = 760 cal.

The value of the equilibrium constant at 927°C is

K = anti 10g[ 4.5;;:1~00]

K = antilog [-0.1385] = 0.7269.

Since all the gases are behaving ideally, we have Putting the value ofK in the above,

P('() PH

K= 1 1

PCOPH,O

Putting the value of K in the above, ?c'o, PHl = 0.7269

?c,()PH,o

(4.C.7)

This is a relation in four unknowns; hence, in order to find out the values of all the unknowns, at least three more relations between them are needed. These can be derived as follows:

(i) The total pressure in the heat-treating furnace is 1 atm, and the gas mixture contains 50% N2; hence,

PH2 + pco + PC02 + Pl120 = 0.5 atm (4.C.8)

(ii) The gaseous system is composed of carbon, hydrogen, and oxygen and the molecular species at equilibrium are CO, CO2, H2, and H20. The total amount of either carbon, hydrogen, or oxygen remains constant throughout, and is independent of the molecular constitution. Hence, three expressions for the conservation of masses of carbon, hydrogen, and oxygen can be derived, which in turn can be expressed in terms of partial pressures.

If the number of g-atoms or molecules of each is represented by n., we have

11C = 11' co + n' CO2 = nco + nC02

nH = 2n'H2 + 2n'H20= 2nH2 + 2nC02 + 2nl-l20

no = n'co + 2n'C02 + n'uzo = nco + 2nC02 + nl-l20

(4.C.9) (4.C.lO) (4.C.ll)

where the primed quantities refer to the gas mixture as analysed and the unprimed quantities to the equilibrium composition of the mixture at 927°C. Since the analyses are given in volume percent, which is proportional to the number of moles, it is convenient to consider a total mass corresponding to 1 mole of the sample as analysed. The number of moles to each constituent

is equal to the volume percent .divided by 100. The number of g-atoms of carbon, hydrogen, and oxygen is conserved throughout, and hence,

nc = n'co + n'C02

60

30 10

=-+-

100 100

=0.4

nH = 2n'H2 + 2n'fUO

20 =-+0 100

= 0.2

no = n'co + 2n'C02 + n'H20

30 20

=-+-+0 100 100

= 0.5

Putting the values ofnc.nH and no in Eqs. (4.C.9), (4.C.IO) and(4.C.l1) nco + ne02 = ne

=0.4.

= 0.2.

nco + 2ne02 + nH20 = no

= 0.5.

-Changing the above equations in terms of partial pressure with the help of equation

P, = _!!_;_.P

nlotal

where P is total pressure, we have pco + PC02 = 0.4,

2PH2 + 2PH20 =0.2, and PCO + 2PC02 + 2PH20 :: 0.5

Thus we have five simultaneous equations relating Peo, PC02,PH20 and Pm, as follows:

PC02 + Pco+ PH2 + PI12U = 0.5, PC02PH2 =0.7269 Pco PH20 Pco + PC02 = 0.4,

2PH2 + 2PH20 = 0.2, and Pco +PC02 + PH20 = 0.5

From the above five equations. the values of Peo, PC02, PJJ2 and PJI20 can be calculated, and the values are

PH20 = 0.024

PH2 == 0.076

Pco == 0.324 and PC02 == 0.076.

In terms of volume percent, the equilibrium composition of the gas mixture is H20 = 2.4%, H2 == 7.()%, CO == 32.4%, CO2 == 7.6% and N2 == 50%.

61

4.4 Van't Hoff Equation

The Gibbs-Helmholtz equation at constant pressure is represented as d(6Go IT) = 6Ho

d(lIT)

Substituting the value of 6GO from Eq.(4.12),

d(ln K) -Wo
=
d(l I T) R
dOn K) Wo
=--
dT RT2 (4.14)

(4.15)

The above equation is commonly called the Van't Hoff equation.

4.4.1. Integration of Van't Hoff Equation

From Eq.( 4.14) it follows that - Rd(lnK) = 6H()d(~-.) T

( 4.16)

6HO is not independent of temperature; hence, in order to integrate the above equation, it must be converted to a form in which there is no term dependent on temperature.

·Since [aMI] = 6C 1'.

aT I'

Assuming that Cp is expressed in the form Cp = a + bT - cr2 ,

we have,

[a6H] A Ab7' A T-?

-- = Da + D - DC -

aT I'

or d6H = (Aa + Ab'T - L\cr2 )dT.

For the standard state also, we have d6Ho = (Aa + 6bT - L\cr2 )dT.

Integrating the above equation,

d6Ho = 6aT + 6bT"_ + 6c + 6Ho (4.17)

2 T

where 6H is an integration constant. Putting the value of 6Ho in Eq.( 4.16),

[ 1] 66 T 2 [1] 6c [1] [ 1 ]

-Rd(lnK)=t,aTd -r +-2-d T +rd T +6H"d T

62

Since d[_!_] = - dT we have

T T2 '

M T. 6.b T 2 6.c, [ I ]

-Rd(lnK)=--df---dT---d7 +6.H d-

T2 2T2 T.T2 .. T

Integrating the above equation,

RI K 6.b Sc 6.H"

- n = -6.alnT -·-T +--+--+ I

2 2T2 T

where I is an integration constant. On rearranging,

6.h Sc 6.H"

- R In K + Sa In T + - T - _ = -- + I

2 2T2 T

( 4.18)

The left-hand side of the above equation is commonly designated as L and is called 'sigma function'.

6.b Sc

Thus, L = -RinK +6.alnT + -T-- 2 2T2

It is evident from Eq.( 4.18) that the equilibrium constant of a reaction at any temperature can be calculated from the heat capacity values of the reactants and products, provided the equilibrium constant values at two different temperatures are known, as illustrated 'in the following example.

Example 4.D

The equilibrium constants for the decomposition of nickel oxide

N i 0 = N i + 12 O2

are 1.514x10-11 and 2.355xIO·g at 527° and 727°C (800 and 1000 K) respectively. Calculate the value of the equilibrium constant at 627°C (900 K) from the following data:

Cp, NiO = 11.18 + 2.02 x 10-31 cal/deg/rnole

(46.78 + 8.45 x 10-31' .IlK/mol) in the range 292° -I 527°C.

Cp,Ni = 7.10 + 1.0xlO-3T -2.23 xlO5T2 calldeg/mole

(4.184x I 0-3T-9.33x l(fiT2 J/K/mol) in the range 357 C -M. P.

Cp02 = 7.16 + 1.0 x 1O-3T-0.-l xl05T2 cal/deg/rnole

(4.1 84xlO-3T - 1.67 xl 05 T2 J/K/moll) in the range 20· -272TC.

Solution:

The heat capacity change for the reaction

is written as

63

£lCp = 2:Cp product - 2:Cp reactant CpNi + Y2 C, 02 - CPNiO

Putting the appropriate values in the above,

£lCp = (7.10 + 1.0xlO-JT - 2.23x10sr2) + Y2 (7.16 + 1.0xlO-3T - OAx10sr2) - (11.18 + 2.02 x10-3T)

= -0.5 - 0.52 x 10-3 - 2.43 x 105r2.

Thus, £la = -0.5, £lb = -0.52x10-3, and £lc = 2.43x10s.

Substituting the values of £la, £lb, and £lc in Eq.( 4.18), and changing to common logarithm,

_ 4.57410g K _ 2.303xO.510g T _ 0.52x1 0-3 T _ 2.43x;OS = £lHo + 1

2 2T- T

(4.D.1)

_ 1.215x10s £lH

or - 4.57410gK -1.511og T - 0.26x1 0 3 T - 2 = __ 0 + 1

T T

Putting the value ofK at 527°C (800 K) in Eq.(4.D.1),

-4.57410g1.514x10-" _1.5110g800_0.26x10-3800_1.215X!OS = £lHo +1

800- 800

On simplification,

£lH" --+1=45.7611 800

Similarly, putting the value of K at 727°C (1000 K) in Eq.(4.D.1),

(4.D.2)

£lH"

-- + J = 31.0655 1000

From Eqs.(4.D.2) and (4.D.3),

£lH" _ £lH II = 14.6956

800 1000

£lH = 800x1000x14.6956

o 200

= 58,800.

(4.0.3)

Substituting the value of £lH in Eq.(4.0.3), 58.80 + 1=31.0655,

or

1= -58.80 + 31.0655 = -27.734.

Substituting the values of £lH and r in Eq.( 4.0.1),

4 5741 K 1 I 6 -3r 1.215x10s 58800

-. og - .51 ogT-0.2 x10 'T- T2 = T -27.734

r 3 1.215x105 6.Ho

or -4.57410gK=-1.5110gT-0.26x10-·T- ? ---+27.734

T- T

64

At T = 627°C (900 K), and on simplification, we have log K = -9.046.

Taking antilogs,

K = 8.995xl0-1O.

The value ofequilibrium constant at 627°C is 8.995xl0-IO•

Exercises

4.1 The equilibrium constant for the reaction (H2) +[O]Fe,wt% = (H20)

in the range of 1563 ° (1836 K) to 1750°C (2023 K) is given by

7,050

logK=---3.17

T

State the expression for 6.0° as a function of temperature. Also, find 6.0° for the reaction Y2 (02)= [O]Fe,wt%

at 1600°C (1873 K) from the following data: (H2) + Y2 (02) = (H20)~

flGo = -60,180 + l3.93T cal (-251,793 + 58.28T J)

4.2 The equilibrium constants of the reactions <FeO> + (CO) = <Fe> + (C02); KI <FeO> + (H2) = <F.;> + (H20); K2

at various temperatures, are gi yen below:

Temp.,oC 600 700 800 900 1000
(Temp., K) 873 973 1073 1173 1273)
K1: 0.900 0.673 0.535 0.453 0.396
K2: 0.332 0.422 0.499 0.594 0.668 Calculate the equilibrium constant of the reaction

at the above temperatures. Also calculate the heat of reaction for the production of hydrogen from carbon monoxide and water vapour, assuming it to be independent of temperature.

4.3 The complete reduction or aW03, takes place in four successive stages, according to the following reactions:

IOaW03 + H2 = 10 W02.9 + H20; KI

65

- 3792

10gKI = +4.6268

T

50 50

"9W029 +H2 = "9W0272 +H20;K2

-1442.5

logK2 = T + 1.684

50 50

-WO?7? + Hz =-WO? + H?O;K, 26 - - 36 - - .>

- 801.7

logK3= T +0.8615

1 1

'2W02 + H2 ='2W + H20;K4

- 2219

logK4 = + l.5809

T

Find an expression for the standard free energy change for the complete reduction of a W03 i.e. aW03 + 3H2 = W + 3 H20

as a function of temperature and, hence, calculate its value at 800aC (1073 K).

-4.4 Calculate the vacuum needed for obtaining molybdenum metal according to the reaction MoS2 = Mo + S2

at 800aC (1073 K) and 1000aC (1273 K).

MoS2 + 2 H2 = Mo + 2 H2S; K1• 2H2S = 2H2 + S2; K1•

Temp., -c : 800 1000

Given:

Temp,K; 2073 1273)

K1 7.3x10-6 1.439x10-3

K2 2.2x 10-4 5.6 x 10-3

4.5 Calculate the CO/C02 ratio in equilibrium with carbon at 727°C (1000K assuming that the total pressure to be 2 atm (202650 N/m2)

Given: 2C + O2 = 2 CO; C + O2 = C02;

~GOIOOO = -95.3 kca1 (-398.7 kJ). ~Goiooo = -94.0 kcal (-393.3 kJ)

4.6 Calculate the equilibrium partial pressure of Zn vapour and CO at l200°C (1473 K)

according to the following reaction:

66

<ZnO> + <C> = (Zn) + (CO);

~Go = 88,720 + 10.35'1' 10gT - 103.33T cal (371,204 + 43.30T 10gT - 432.337T J).

Assume that the reaction is carried out in a closed retort containing no air.

4.7 Evaluate the partial pressure ofMg vapour at l200°C (1473 K.) for the following reaction:

2<MgO> + 2<CaO> + <Si> = 2(Mg) + <2CaO.si02>.

Given: 2 <MgO> + <Si > = 2(Mg) + <Si02>;

~Go = 152,600 + 11.37T log T - 99.18Tcal (638,478 + 47.57 T tog T - 414.97T J).

2< Cao>+<Si02> = <2 CaO-S 1 02>;

~GO = -30,200 - 1.2 T cal (-126,357 - 5.02 T J).

4.8 In a copper converter, the following reaction is believed to occur in the latter stages: (CU2S) + 2(Cu20} = 6{Cu} + (S02);

~Go = -87 - 5.l3Tcal (-364 - 21.46TJ).

Calculate the equilibrium partial pressure of SO, at 1250°C (1523 K). Assume that both Cu2S . and Cu20 exist as pure melts.

4.9 Will a magnesia crucible decompose at 1000°C (1273 K) in a vacuum of 0.01 atm (1013 N/m2)?

Given:

~GO = 145,350 + 0.24T 10gT - 26.95 T cal (608,144 + 1.01 10gT - 112.75 T J).

4.10 Win a blast furnace gas analyzing 28% CO. 13% C02 and 59% N2 reduce wustite (FeO) at 727°C (1000 K)?

Given: <Fe> + Y2 (02) = <FeO>;

~Go = -62,050 + 14.95 T cal (-259,617 + 62.55 T J). (CO) + Y2 (02) = (C02);

~Go = -67,500 + 20.75 Teal (-282,420 + 86.82TJ).

4.11 Calculate the equilibrium constant at 727°C (1000 K) for the reaction <FeO> + (CO) = <Fe> + (C02)

from the following data:

67

<FeO> + (H2) = <Fe> + (H20);

l1Go = 3,150 - l.85 Teal (13,180 - 7.71 TJ). (C02) + (H2) = (CO) + (H20);

l1Go = 8,600 - 7.8 Teal (35,982 - 32.63 TJ).

Will F eO form if an iron sheet is annealed at 727°C (1000 K) in an atmosphere containing 10% CO, 2% CO2 and 88% N2?

4.12 One stage of an industrial process involves the drying of moist silver carbonate in an air stream at 110°C (383 K), without decomposing it according to the following reaction:

Ag2C03 = Ag20 + CO2;

l1G0383 = 3.512 kcal (14.69 kJ).

Calculate the minimum partial pressure of CO2 which must be introduced into the stream of air used.

4.13 Chromium plates are bright annealed at 727°C (1000 K) in a wet hydrogen atmosphere. The pressure of wet hydrogen is 1 atm (101,325 N/m2)

(i) Calculate the permissible water content in the hydrogen if there is to be no oxidation at 727°C, (1000 K).

(ii) Will annealed chromium plates be oxidized when cooled to 227 C (500 K) in the furnace atmosphere, as calculated in (i)?

Neglect the possibility of dissolution of hydrogen in chromium.

Given: 2<Cr> + 3(l-hO) = <Cr203> + 3(H2); l1Go = -91,050 + 22.80 T cal (-380,953 + 95.4TJ).

4.14.Determine the lowest temperature at which copper oxide (CU20) can dissociate in a vaccum of 10-5 mm Hg.

Solution: The basic step in calculating the minimum temperature for a reaction to proceed is to determine the free energy change for the reaction as a function of temperature. Under a particular set of conditions, the minimum temperature is that at which the free energy change is related to the value of the equilibrium constant for the reaction by equation

The dissociation reaction:

llGO = 40500 + 3.92TlogT - 29.5 T cal

68

112 2

!:!.GO = -RTln 1m at,,, aCu2()

1/2 = - 4.S7Slogp02

Assuming that the Cu and CU20 are in the pure state (i.e. a =1), and the oxygen behaves as an ideal gas.(f02 = P02) In a vaccum of 10-s mm Hg , taking the partial pressure of oxygen in air as 0.2 atmosphere:

P02= O.2xlO-s xl1760 = 2.63Sx10-9 atmosphere

therefore

!:!.G' = -2.288T log (2.63Sx1 0-9) = 19.6T

The maximum temperature tel for dissociation of CU20 is given by

40S00 + 3.92TlogT - 29.S T = 19.6T 40S00 + 3.92TlogT - 29.S T - 19.6T = 0

which is best solved graphically _ (40S00 + 3.92TlogT - 29.S T - 19.6T) versus T, the minimum temperature of dissociation of CU20 is obtained as the intersection of the X axis.

T = 108S K

4-1S.In separate experiments. pure nitrogen at atmospheric pressure is passed over either 'mercury or a mercury _ thallium amalgam (68.4 atom percent thallium). At temperature less than 100°C the vapor pressure of thallium is negligible, relative to that of mercury. The flow rate of the nitrogen is controlled such that the gas is just saturated with mercury vapor as it passes over the pure mercury or the mercury or the amalgam. The vapor carried over in the gas stream is condensed in a cold trap and weighed. In experiments with the samples at 26°e, the weights of mercury trapped from the pure mercury and the amalgam were respectively 2.20 and 0.7Smg per hundred liters of nitrogen, the nitrogen volume being measured at 200e and 1 atmosphere pressure. Assuming that equilibrium is continuously maintained over the samples, calculate the partial pressure of mercury over the amalgam and the activity coefficient of mercury in the amalgam at 26' C.

Solution: This example is concerned with the carrier-gas experiment, where the partial pressure of a volatile component over a solution is measured by sweeping away the vapor of the component, under equilibrium conditions, with an inert carrier gas and weighing the condensate. The activity of the volatile component in the solution is directly calculable from measurement of the partial pressure of the component over the solution and over the pure component. The reactions may be written as follows. For pure mercury:

Hg (pure,!) = Hg (g, in N2)

[f J

K = Hg

p a

Hg (pureHg)

= PHg(pure Hg)

69

Assuming that mercury vapour behaves as an ideal gas, and as aHg == I when referred to pure liquid mercury as the standard state. Over the amalgam:

Hg (I, in amalgam) == Hg (g, in N2)

(PHg]

Kp ~ aHg (amalgam)

again assuming that the mercury vapour behaves ideally. Since the equilibrium constant K for a reaction in a system is independent of the initial composition of the system, it follows that:

p Hg(amalgam)

a ---~~--~~

Hg(amalgam) - p

Hg(pure,Hg)

The volume of nitrogen was measured at 20oe, whereas the experiment was performed at 26°C. This latter is the temperature for which the partial pressure must be calculated. Thus(assuming the nitrogen behaves ideally)

.Volume (of 100 liter at 200e) at 26°e == 100 x (2991193) == 102 liter

When passed over the pure mercury, this volume of nitrogen contains 2.20 mg mercury. As 200.6 g of mercury (== gram atomic weigh of Hg) occupies 22.4 liter volume at NTP, therefore:

2.2 mg Hg occupies (22.4/200.6)x2.2 == 0.239 cc at N.T.P.

== 0.239 x (299/273) cc at 26°C

== 0.262 cc at 26°C

Thus, the partial pressure of Hg over pure mercury

0.262

== x760

102000

= 19.5xl0-4 mm Hg

When passed over the mercury-thallium, 102 liter of nitrogen contains 0.75 mg mercury, which occupies a volume of:

70

22.4

-- xO.75cc = 0.082cc.aLN.T.P. 200.6

= 0.089 cc at 26°C

Thus, the partial pressure of Hg over the Hg , TI amalgam

0.089

= x760

102000

= 6.65x I 0-4 mm Hg

Therefore,

6.65x10- 4

= = 0.34

19.5x10- 4

And

a

=~= 0.34 =1.08

YHg N 0.316

Hg

4-16. A methane-hydrogen mixture at 1 atmosphere pressure is allowed to come to equilibrium with a steel containing 0.60 weigh-percent carbon at 925°C. On analysis, the gas is formed to contain 0.64 % methane and 99.36% hydrogen by volume.

Calculate the activity of carbon in the alloy and the expected analysis (by volume) ofa carbon monoxide mixture which would be in equilibrium with the steel at the same temperature and pressure.

Solution:

C(s,graphite) + 2H2 (g) = CH4(g)

t.GO = -21,600 + 26.2 T cal

t.GO = -RT InKp

Therefore K, = 0.0162

When the gases are assumed to behave ideally. Substituting the given gas composition in equilibrium with the steel:

71

K f' = 0.162 = 0.006~ (0.9936t ae

a. = 0.0064 = 0.40

G 0.0162(0.9936)~

i.e. activity of the carbon in the steel, relative to graphite as the standard state, is OAO.

The composition of carbon monoxide-carbon dioxide atmosphere in equilibrium with carbon at this activity is obtained from the equilibrium constant for the reaction:

C02(g) + C (s,graphite) = 2CO ~Go = -21,600 + 26.2 T cal

K, = 48.6

at 1198 K

2

P C()

Pcma(.

2

K f' = 48.6 = P co PU)2 OAO

2

P cn = 18.72

PC02

and Peo + Pe02 = 1

Peo = 0.952 atm

Pe02 = 0.048 atm

That is, a gas comprising 95.2% CO and 4.8% C02 (by volume) at 1 atm pressure is in equilibrium with the steel containing 0.60 weight percent at 925°C.

4.17. The stability of ammonia gas depends on pressure as well as on temperature. Show that this

is so by calculating the extent of the dissociation of ammonia to form hydrogen and nitrogen at 200°C at 1.0 and 0.8 atmosphere pressure.

Solution:

~GO = 10,400 + 7.1 Tlog T - 3.79 T cal

At 473K

.6.GO = -380 cal

and K, = 1.49

(1)

if the gases are assumed to behave ideally.

The two additional relations between the partial pressures are obtained by consideration of the restrictions on the system. Thus, as the dissociation of ammonia always results in the

72

formation of3 mole of hydrogen to 1 of nitrogen, it follows that:

(2)

In addition, the total pressure is fixed at first 1.0 and then 0.8 atm pressure;

i.e. for 1 atm pressure.pu- + PH2 + PNH3 = 1 (3)

PH2 = 0.63,

PN2= 0.21 and PNH3 = 0.15

Hence 1 atm pressure, 84.5 % (by volume) of the ammonia will dissociate.

When the total pressure is 0.8 atm.

PH2 = 0.52,

PN2 = O. 1 7 and PNH3 = 0.10

Hence 0.8 atm pressure, 86.4 % (by volume) of the ammonia will dissociate.

4.18. The equilibrium between carbon and its oxide is such that above about 900°C the formation of carbon dioxide is negligible at 1 atmosphere pressure. With this in mind, calculate the approximate minimum temperature for the reduction of pure manganese oxide by solid carbon to form pure manganese metal in a vaccum of 10-3 mm Hg. If the reduced metal .enters into solution in iron and the minimum temperature of reduction is thereby lowered 53·C, calculate the activity of the manganese in solution in the iron.

MnO (s) = Mn (s) + I/Z 02(g) : flO·= 91950 - 17.4T cal (1)

C(s) + ~ 02(g) = CO(g) : flO· = - 26,700 - 20.95T cal (2)

From equation (l) & (2)

MnO (s) + C (s)= Mn (s) + CO(g) flO· = 65,250 - 38.35 T cal

The minimum temperature for the reaction to proceed will be that at which this expression equal (-RT InKp) for the reaction.

65250 - 38.35T = -4.574T log i(,()aMII

aMII()ac

= - 4.575T logpco

when all the condensed phases are pure and the carbon monoxide behaves ideally. Thus:

10-3 65250 - 38.35T = -4.574T log- 760

73

T = 1000 K

The solution of the manganese in the iron results in a depression of the minimum temperature of reduction by 53°C, i.e. this temperature becomes 94TK

65250 - 38.35x947 = -4.574x947T logPcoQMn

The activity of the manganese in solution in the iron is 0.159.

74

ANSWERS TO THE CHAPTER 1

(1.1) -302.49 kcallmole of 8203, -4.343 kcallg of 8203. (1.2) (i) 8940 kg, (ii) 15285 kg, (iii) 12745 kg.

(1.3) -8878 kca11l00 kg of ore.

(1.4) -6.5 kcal.

(1.5) 318.6 kcal.

(1.6) (a) -35.79 kcallmole, (b) 21.71 kcallmole. (1.7) -69.25 kcal, -66.0 kcal.

(1.8) -57.98 kcallniole.

(1.9) -211.9 kcal, -212.85 kcal.

(1.10) flHTo = (0.58x10-3T2 - 3.66T - 4.17xI05y-l + 59240) cal.

(1.11) HOT - H029s, = 5.335 (T-298) + 3.74x 10-3 (T2 -2982) callg-atom, Cp = (5.335 + 3.74x10-3T) calldeg/g-atom.

(1.12) 62.76 kca1/mole, 2.549 kcallmole.

_( 1.13) 1511 kcallkg of zinc.

(1.14) -27.85 kcal.

(1.15) 328 kcallkg of scrap. (1.16) -223.08 kcallmole ofTi02• (1.17) -93.17 kcallmole of MoO.

( 1.18) (a) 2031 °C, (b) 2956 cal/cu.ft. of exhaust gas. (1.19) - 66.1 kcal

(1.20) - 35.4 kcallmole of Zn

ANSWERS TO THE CHAPTER 2 (2.1) Zero.

(2.2) (a) ~H = 125,000 cal, ~s = 129.23 calldeg. (b) ~H = 329,000 cal, ~s = 138.33 calldeg. (2.3) 7.07 calldeg/mole.

(2.4) 0.121 calldeg/mole, process spontaneous.

75

(2.5) -79.94 calldeg. (2.6) 0.35 calldeg. (2.7) 0.218 calldeg.

(2.8) -16.5 kcallmole of Mo, 34.5 kcallmole of Cr, not possible to reduce Cr203 by H2, (2.9) 1420°C.

(2.1 0) 572.5°C.

(2.11) 3.5°C.

(2.12) At or above 1472°C. (2.13) Titanium.

(2.14) Not possible.

(2.15) Copper.

(2.16) Not spontaneous. ANSWERS TO THE CHAPTER 3 (3.1) 99 kcallmole

(3.2 32.2 kca1/mole.

(3.3) 2577°C.

(3.4) 27.35 kca1/mole. (3.5) 269.65°C.

(3.6) 321.006rC, 320.9933°C. (3.7) 6.265 xlO-3 degiatm.

(3.8) 818°C.

(3.9) 3.732x10-3 DC, -0.7463°C. (3.10) -6.012°C.

(3.11) 0.5210 mm Hg.

ANSWERS TO THE CHAPTER 4

(4.1) 60° = -32,250 + 14.51T cal, -29,016 cal.

(4.2) 2.711. 1.595, 1.073, 0.7626,0.5928, 6Ho = -8320 cal. (4.3) 6Go = 25,840 - 20.89 T cal. 3420 cal.

76

(4.4) 1.608xlO-9 atm, 8.058x10,6 atm. (4.5) 1.57.

(4.6) l3.40 atm each. (4.7) 8.71 x10-3 atm. (4.8) 13.58 atm.

(4.9) Will not decompose. (4.10) Will reduce.

(4.11) 0.78, no.

(4.12) 7.53 mm Hg

(4.l3) < 1.072x 10-3 vo 1 ume% H20, oxidise.