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Chap 6 Tasmo Tami Selvi Evelyn

Chap 6 Tasmo Tami Selvi Evelyn

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CHAPTER

SIX

HEAT CAPACITY, ENTHALPY, ENTROPY,
AND THE THIRD LAW OF THERMODYNAMICS
6.1
INTRODUCTION Equations (2.6) and (2.7) defined two heat capacities, the heat capacity at constant volume (2.6) and the heat capacity at constant pressure (2.7) At this point it is convenient to introduce a notation which will allow distinction to be made between the values of extensive properties per mole of a system and the values of extensive properties for the entire system. If E is an extensive property, then E' will be taken as denoting the value of the property for the system containing n moles, and E will be taken as denoting the value of the property per mole of the system. Thus, for a system containing Il moles. E'=nE
113

114

METALLURGICAL THERMODYNAMICS

Equations (2.6) and (2.7) can thus be written equivalently as, dU'

= CvdT = ncvdT

or or

dU

= cvdT

(2.6a) (2.7a)

dH' = CpdT = nCpdT

dH = cpdT

where cp and Cv are, respectively, the constant-pressure, and constant-volume molar heat capacities. Integration of Eq. (2.7a) between the states (Tz, P) and (TJ, P) gives, f:::.H =H(Tz ,P) - H(TJ ,P)

r = l:

T2

cpdT

(6.1)

T,

from which it is seen that a knowledge of the temperature dependence of cp is required for the determination of the temperature dependence of the molar enthalpy, and, as will be seen, for the determination of the temperature dependence of entropy. Similarly, integration of Eq. (2.6a) between Tz and T, at constant volume indicates that the determination of the temperature dependence of internal energy requires a knowledge of the temperature dependence of cv'

6.2 THEORETICAL CALCULATION OF
THE HEAT CAPACITY
In 1819 Dulong and Petit introduced the empirical rule that the molar heat capacities of all solid elements equalled 3R (= 24.9 joules/degree). Subsequent experimental determination of values of the heat capacities of various elements showed that the heat capacities always increase with increasing temperature and that the values tend to be much lower than 3R at low temperatures. Also the heat capacities can be higher than 3R at temperatures greater than room temperature. Figure 6.1 shows the variation of Cv with temperature for several elements. Calculation of the heat capacity of a solid element, as a function of temperature, was one of the early triumphs of the quantum theory. The first such calculation is due to Einstein, who considered the properties of a crystal comprising n atoms, each of which, in classical terms, is considered to behave as a harmonic oscillator vibrating independently about its lattice point. As each oscillator is considered to be independent. i.e., as its behavior is unaffected by the behavior of its neighbors, then each oscillator vibrates with a single fixed frequency v, and a system of such oscillators is known as an Einstein crystal. Quantum theory gives the energy of the ith level of a harmonic oscillator as (6.2)

...

HEAT CAPACITY. ENTHALPY. ENTROPY AND THE THIRD LAW

115

25

e
CI) CI)

20 15

Cl

~
CI)

.2- 10

:l

J

5

Temperature,

K

Fig. 6.1. The constant molar volume heat capacities of Pb, Cu, Si, and diamond as a function of temperature. (From E. D. Eastman and G. K. Rollefson, "Physical Chemistry," Mctlraw-Hili Book

Company, New York, 1947.)

where i is an integer which can have values in the range zero to infinity, and h is Planck's constant of action (= 6.6252 X 10-34 joule·s). As each oscillator has three degrees of freedom, i.e., can vibrate in the x, y, and z directions, then the energy U' of such a system (which can be regarded as being a system of 3n linear harmonic oscillators) is given as (6.3) where, as before, Ili is the number of atoms in the ith energy level. Substituting Eqs. (6.2) and (4.13) into Eq. (6.3) gives

U' = 3 ~ (i + 1) hv [
=3nhv
~

ne-h

v (i + ~

)/k TJ
1 l)/kTj -2 ~e- h viiI + '2 v

~e-hv(i
'2
1

+ ~)/kT

~le-

. h v (.I +

)/kT

~e-hv(i ~ie-hvi/kT [ ~e-hvi/kT

+ ~)/kT ]

+ -------

~e-hv(i

+ ~)/kT

= 3nhv

+.!

2

= ~ nhv
2

[

1+

2~ie-hvi/kTJ "-----~e-hvi/kT

Taking

116 where x = e-hv/kT gives

METALLURGICAL

THERMODYNAMICS

x(I + 2x

+ 3x2 + ... ) =

x (I- X)2

and

Le-hvi/kT

=

Lxi

= 1 + x + X2 + ... = __ 1__
(I-x)

in which case

U'

= ~ nhu ~
2

L + - 2x I-x
+

J J
(6.4)

3 =2

nhu ~1

hv kT 2e- / 1 _ e-hv/kT

=

.2 nhu
2

+

3nhv (ehv/kT - 1)

Equation (6.4) then expresses the relationship between the energy of the system and the temperature. Differentiation of Eq. (6.4) with respect to temperature at constant volume gives, by definition, the constant-volume heat capacity Cv (as the volume remains constant, then so the quantization of the energy levels remains constant). Thus

Cv

= -a- =
Tv
=

(au')

3nhv(ehv/kT

-lr

2

!!:!!....ehv/kT kT2

hV)2 3nk ( kT

ehv/kT (ehv/kT _1)2
and heat

Defining hulk = BE' where BE is the Einstein characteristic temperature, taking n equal to Avogadro's number gives the constant-volume molar capacity of the substance as

(6.5)

ENTROPY AND THE THIRD LAW 117 The variation of Cv with Tie E is shown in Fig.5) to experimentally measured heat capacity data.0 Tie Fig. the theoretical values approach zero significantly more rapidly than do the actual values. and as T ~ 0.2) shows that.2 . of frequencies available to the oscillators is the same as that available to the elastic vibrations of a continuous solid. if the wavelength was equal to the interatomic distance.6 . 6. i.2. Such curve fitting (see Fig.4 . Comparison among the Debye heat capacity. The next step in the development of the theory was made by Debye. Taking this minimum wavelength Amin to be in the order of 5 X 10-8 cm and 20 '0 E Cl OJ OJ e :l OJ 15 @ AI eo = 385 K ~ . then successive atoms would be in the same phase of vibration. or spectrum. hence vibration of one atom with respect to another. Cv ~ 3R in agreement with the Dulong and Petit law. are obtained by curve fitting Eq.8 1.. which shows that as Tie E (and hence T) increases. and its vibration frequency u. 10 J 5 o .2.4 1. in which case neighboring atoms vibrate in opposition to each other. and the actual heat capacity of aluminum. Theoretically the shortest allowable wavelength is twice the interatomic distance. which is termed the Einstein characteristic temperature for that element. This discrepancy between theory and experiment is due to the fact that the oscillators do not all vibrate with a single frequency. the Einstein heat capacity. the lower limit is fixed by the interatomic distances in the solid. 6. The actual value of e E for any element. With respect to the wavelengths of these vibrations. ENTHALPY. 6.2 1.e.0 1.!':! . as such.HEAT CAPACITY.2. would not occur.8 2. Cv ~ 0 in agreement with experimental observation.6 1. . although the Einstein equation adequately represents the actual heat capacities at higher temperatures. (6. who assumed that the range.

which shows good agreement with the theoretical maximum frequencies of elastic vibration in a solid.6) in comparison with the Einstein equation. Column 1 gives 8D as determined from "best fit" between theory and measurement over a temperature range in the vicinity of 8D/2. "o. Eq. where the heat capacity is fairly large.118 METALLURGICAL THERMODYNAMICS the wave velocity v in the solid to be 5 X 105 cm/sec gives the maximum frequency of vibration of an oscillator to be in the order of Vrnax = _v _ = \nin 5 X 10-8 2J< 10 5 = 1013 sec " Debye assumed the frequency distribution to be one in which the number of vibrations per unit volume per unit frequency range increases parabolically with increasing frequency in the allowed frequency range 0 ~ v ~ vrnax.6) gives Cv = 1943 (8:) 3 joules/degree (6. Table 6.7) is of particular use at temperatures below those at which the heat capacity has been measured experimentally for a given material. (6. with x = hulk/I'. gives (6. Equation (6.2 illustrates Eq. (6.vary from 3.83 X 1012 seCI for lead. and column 2 gives 8D from the "best fit" of the low-temperature data and Eq. (6.6) where "o (the Debye frequency) = vrnax' and 8D = hVD/k is the characteristic Debye temperature. (6. as is seen. The Debye frequencies. For very low temperatures Eq. and. Figure 6.7) which is termed the Debye t" law for low-temperature heat capacities.84 X 1013 sec-I for diamond to 1. and by integrating the Einstein expression over this frequency distribution.1 lists the Debye temperatures for a number of elements for which the constant-volume molar heat capacities have been accurately measured. . he obtained the heat capacity of the solid as which.6) gives an excellent fit to the experimental data at lower temperatures.7).

" Mc Graw-Hill Book Company. Ag. and C( diamond) with the Debye equation. ENTHALPY.. 6. molar heat capacities of several solid elements.. K.HEAT CAPACITY. Al.4. Figure 6.3 shows that when the experimental data is plotted as a function of log T. (From E. Eastman and G. ENTROPY AND THE THIRD LAW Table 6. The constant-volume are from the Debye equation Rollefson. Debye's theory does not consider the contribution made to the heat capacity by the uptake of energy by the electrons.2- '" '" J eo = 1. . New York. 6.:. 1947. and suitable choice of a characteristic Debye temperature for each element gives coincidence of the Cv -log TieD plots shown in Fig.3. in any temperature range where the energy associated with the electrons 30 r---------------------------r--------------------------- -6 E 25 ~ '" ~ Ol '"20 15 10 C(diamond) :.1 Substance Pb K Na Sn Cd Au Ag Pt Zn Cu Mo Al Fe C(diamond) eD(high 119 n eD(from T 3 ) 90 K 99 159 160 160 180 213 225 235 315 379 389 420 1890 127 K 129 162 205 321 379 385 428 2230 Figures 6. and since Cv = (3UI3T)v' it follows that. iii!i . the lines produced are nearly identical except for a horizontal displacement. "Physical Chemistry.3 and 6.890 5 Fig.1>':.) Ii lilli' '1IllIlililll .. The curves with the eD values given.4 illustrate the curve fitting of experimental data for Pb. The relative horizontal displacement is a measure of log 0 D for the particular element.. D.

Phys. Eastman and G. K. 1947. Rollefson. "Physical Chemistry.2 +0. A. The variation of Cv with log (Tie D) for several solid elements. K 3 4 Fig.6 log TIe L-I -0.. New York.s J 0.5a..6. Hence the electronic contribution becomes large in absolute value at elevated 0.) changes with temperature..002 o .0 ~I -0.b e a . Rev. (From A. (From E. 10 I- J 51~o ~..IL- __ 2 T.L-__ (fused) (powdered) -L_.2 Fig.. Daunt.004 :. D.. The low-temperature constant-volume molar heat capacity of zinc. Silvidi and J.4..l ___.) .008 -5 E CIl 0.120 25 I- METALLURGICAL THERMODYNAMICS I I I o ~ 20 to E CIl q ~ 15 ICIl ~ CIl ]. G. . Consideration of the electron gas theory of metals indicates that the electronic contribution to the heat capacity is proportional to the absolute temperature.-""------Lo -~ ---~~ 6 o . a contribution to the heat capacity will result.4 ~I -1. Electronic Specific Heats in Tungsten and Zinc.. 77:125 (1950J." McGraw-Hill Book Company. 6.006 ~ OJ Cll Cll e '" 0. 0< ~ oq eq • AI b q Pb a Diamond eu _J O~~~~O_~ -1.

) temperatures and also becomes large compared with the atomic vibration contribution (which is proportional to T3) in the temperature range 0 to 1 K. (From A.Sb. Phys. 77:125 (1950/. The curves in Fig.5a and b are represented by v = 1943 (2~1)3 C + 6. The low-temperature constant-volume molar heat capacity of tungsten.Q. This is illustrated by the low-temperature Cv data for Zn and W shown in Fig.5a and b .04 . Daunt. ReF .06 Q.) ~ Cl :2_ Q. 6. respectively. If this interpretation is taken at face . J 0. 6.02 / / / / / / / / / / / / / °0~-------L--------2L-------~3~------~4 T.HEAT CAPACITY.28 X 10-4 Z'joules/degree-mole for Zn and Cv = 1943 C~9r + 214 X 10-4 Tjoules/degreeomole for W In both equations the first term on the right is the lattice contribution and the second term is the electronic contribution.1 0.. where it is seen that the curves approach straight lines with a nonzero slope at 0 K.) ~ 0. C. ENTROPY AND THE THIRD LAW 121 0. K Fig. A.) ~ 0.08 Q. Silvidi and J.6. ENTHALPY.

5 X 105 T-2 joules/degree-mole from 737 K to the melting temperature. and b has the same value as does the coefficient of T in the low-temperature equation. two equations are used: o-Ca cp = 22. normal practice to experimentally determine the cp-T variation of a substance and express the relationship analytically. and the requirement of a knowledge of the variation of the heat capacity with temperature for the determination of the temperature dependence of en thalpy and entropy. i.e. then at high temperatures. for Ca. 603 EMPIRICAL REPRESENTATION OF HEAT CAPACITIES The experimentally measured variation of cp for a substance with temperature is normally fitted to an expression of the form Cp = a + bT+ c'T -2 and it is to be noted that the analytical expression is only applicable in that stated temperature range over which the CD values were measured. where the lattice contribution approaches the Dulong and Petit value. Often.122 METALLURGICAL THERMODYNAMICS value. Ca has a high-temperature allotrope (the {3-phase) which is stable above 737 K and a low-temperature allotrope (the o-phase) which exists below 737 K.3 + 32. e. Hence.4 X 10-3 T + 10. That this is not borne out experimentally is not particularly surprising in view of the difficulty of determining the number of electrons per atom present in the electron gas. at present.. it is.9'" 10-3 Z'joules/degree-moje over the temperature range 273 to 737 K. in which case cp is expressed as a . the number of electrons per atom making a contribution to the heat capacity. as for example with o-Ca.94 + bT joules/degree-mole where bT is the electronic contribution. Also the anharmonicity of the lattice vibrations makes a contribution to the heat capacity at elevated temperatures. it would be expected that Cv could be represented as Cv = 24.g.. and {3-Ca cp = 6. cT.. the accuracy of measurement does not 2 warrant inclusion of the third term. In view of the discrepancies between the theoretical calculated values of heat capacities and the experimentally determined values.2 + 13.

18 X 1O-3T-1.79 + 4. ENTROPY AND THE THIRD LAW 123 35 CL> 30 "0 CL> E 25 ~ Cl CL> 20 15 ~ ~ :l . i.2 X 10-3T-6.19 X 1O-3T + 6.3000 .25 + 5.mole) 20.2C. ENTHALPY. and from 298 K to the melting temperature the straight-line variation is given as cp = 24. Where the experimentally measured data is insufficient to allow determination of the temperature dependence of cp. is omitted from the analytical equation.5 38 7.3 22.7. The constant-pressure molar heat capacity of platinum.2 30.7 X lO'T-2 X lO'T-2 X 10' T-2 298 Tm 298 Tm 298 Tm 273 1033 1181 1674 Tm 298 298 298 -Tm -1273 -Tm -1600 -Tm -1600 -1033 .Tm -1873 -1200 . cp is assumed to be constant.e.0 Temperature range.2300 .8 X 1O-3T + 19.9 41. 6. The variation of cp with T for several elements at temperatures above room temperature is shown in Fig.3 23. b'I'.19 + 4.376 X 10-3 T joules/degree-mole. linear function of temperature over the stated temperature range. 6.2 Element Al (solid) Al (liquid) Au (solid) Au (liquid) Cu (solid) Cu (liquid) Fe (o) Fe ((3) Fe (-y) Fe (8) Fe (liquid) C(diamond) C(graphite) 02 (gas) cp (joules/degree.6 31.1181 -1674 .4 X 1O-3T + 5.5 X 1O-3T + 13. the second term.2.6 shows the cp-T variation for platinum. Table 6.12 17. 10 o 5 500 Temperature.7 29. Figure 6.27 X 1O-3T-8.6.4 17. "c 1000 1500 Fig.28 X 10-3T + 24. K + 12.7 29.HEAT CAPACITY. as is often the case with liquid metals.70 43. and the corresponding analytical representations of these data are listed in Table 6.8 9.

j:>o 45 40 35 Cu(1) 30 0 E OJ w Au(l) e w 25 C (graph ite) 20 OJ ~ '" "3 OJ . The constant-pressure molar heat capacities of several elements. 15 10 5 L-___L __ -L__ ~L_ ~L___J 0 _J L_ __ __ ~ __ _L L_ __ _L __ _J ~ __ _L __ 400 600 800 1000 Temperature. 6. N .Q.7. ._. o 0. K 1200 1400 1600 1800 Fig.

MiT! =HA(l)(T1)-HA(S)(Td In Fig.1) Mi is thus the area under the cp-T curve between the limits T.g. Mi(T.7a) gives Eq. to T2 at the constant pressure P. (6. . and if Mi < 0. (2. P) = H AB(T. the reaction A + B = AB. For a system undergoing a chemical reaction or phase change at constant temperature and pressure. (2. the melting of pure A. (6. This rule.7) Mi = qp which is simply the amount of heat required to raise the temperature of 1 mole of the system from T. 6. and T2.8) is a statement of Hess's law.HEAT CAPACITY. or change of state. P) .. which is known as Kopp's rule. for this process equals the difference between the molar enthalpies of A(!) and A(s) at the temperature Tl . Thus if there are n atoms in the formula of the compound. the heat entering or leaving the system. the heat capacity per mole is 3nR. Enthalpy changes resulting from temperature and/or composition changes can be represented on an enthalpy-temperature diagram. the reaction occurs with an absorption of heat from the constant-temperature heat bath surrounding the system and hence is an endothermic process or reaction.8) Mi is the difference between the enthalpy of the products of the process (state 2) and the enthalpy of the reactants (state 1). MiT. P) .l ). (6. 6.e. involving the phase change A(s) = AU)' i.. This convention corresponds to that used in connection with the First Law for the sign of q. integration of Eq. and from Eq. is reasonably reliable for ionic compounds at temperatures where the constituent elements of the compound obey the Dulong and Petit law. If Mi> 0. and Eq. Consider the process.HB(T. the reaction occurs with an evolution of heat and is thus an exothermic process. e.8 this enthalpy change is represented by the line ba.H A (T. ENTHALPY" ENTROPY AND THE THIRD LAW 125 In 1864 Kopp proposed that the heat capacity of a solid compound is equal to the sum of the heat capacities of its constituent elements. P) (6.4 ENTHALPY AS A FUNCTION OF TEMPERATURE AND COMPOSITION For a closed system of fixed composition undergoing a temperature change from TJ to T2 at the constant pressure P.

. Fig. T c P A(I) dT the molar heat capacity of liquid A . Temperature .) (T. till(d till(c c) b) = = =- i z TZ 1 T c PA(I) dT = c p AU) = f T.) T..126 METALLURGICAL THERMODYNAMICS HA (I) (T z ) - --- - - - - - - - - - - - - c t > s: w "iii 0. temperature of the solid and For the phase change occurring at the temperature T2. HA (I) (T.) C HA HA (5) (5) (T.8 by the line cd. The variation with liquid phases of a substance. of the enthalpies Solid I I I d T. which is represented in Fig. 6.. 6.. As H is a state function. then M(a where M(a --+ --+ b) = M(a --+ d) + M(d --+ c) + M(c --+ b) d) = the heat required to raise the temperature of I mole of solid A from TJ to T2 cp A(s) --+ --+ = the molar heat capacity of solid A tillT 2 the negative of the heat required to raise the temperature of 1 mole of liquid A from TJ to T2.8.

(a) The variation with temperature of the enthaipies of Pb(s). Pb(/). Yz02. and . (b) The variation with temperature of the enthaipies of (pb + Yz02) and PbO.K __ 500 700 (b) 900 1100 Fig.I a ---+-------------~I I I I I I I I J I I 300 500 700 (al 900 1100 300 T.9. PbO(s). 6.

9. D. which is drawn for the oxidation.128 METALLURGICAL THERMODYNAMICS Thus + or iTz c T 1 PA(s) d'I>: IT2 T 1 c PA(l) dT (6. is independent of temperature. M(solid) + 102(gaS) = MO(solid) at 298 K and as HM .. 298 are. 298 and Ho 2. that is. Thus the enthalpy of a compound at 298 K simply equals the heat of formation of the compound from its elements at 298 K. equals cp for liquid A.e. by definition.HTJ. then The variation of heats of chemical reaction (or heats of formation) with temperature at constant pressure can be represented on an enthalpy-temperature diagram such as Fig.. As the absolute value of H for any state is unknown (only changes in H can be measured).HT2 = D. It is to be noted that if /:"cp = 0. (aH/anp for the liquid A. equal to zero.H. i. Pb + ~02 = PbO . This convention assigns the value of zero to the enthalpy of elemental substances in their stable states at 298 K (25°C). 6. then D. the heat of reaction. e.9) where Thus if the heat of the reaction is known at one temperature and the constant-pressure heat capacities of the products and reactants are known (along with the temperature dependencies of these heat capacities). In Fig. by convention.8 the slope of the line bc . 6. then the heat of reaction at any other temperature can be calculated.g. Thus be is a straight line only if cp is independent of temperature. it is convenient to introduce a convention which will facilitate the comparison of different H-T diagrams.

of H102 (g) with temperature 2 in the range HpbO(s).T'.T ac represents T'. of 600 K Tm.3 HpbO(298) = -219..2 = 23. O (g) joules/mole X 10-3 T joules/degree-mole from 298 K to T m. g represents the enthalpy of I mole of PbO(s) at the temperature T. Pb(s)dT.4 . 600..9a..3.1 X 10-3 T joules/degree. T m.9b. 1159 where HpbO(s).000 joules.8 X 10-3 T joules/degree. PbO(s) dTjoules/mole In Fig. is given as~ f2~8 Cp. ab represents the variation of Hpb(s) with temperature in the range 298'. PbO seeTable 6. 6. Pb(l) 2 cp.. mole from 298 K to T m. PbO = 1159 K t!Jlm ' Pb = 4810 joules/mole at the melting The pertinent thermochemical In Fig.02(g)dT.. a represents the enthalpy of ~ mole of oxygen gas and I mole of Pb(s) at 298 K. ENTROPY AND THE THIRD LAW 129 Table 6. f represents the enthalpy of ~ mole of O2 (g) and 1 mole of Pb(s) at the temperature T. ENTHALPY..298 = -219..75 The latent heat of melting of Pb.298 298'. PbO(s)dT . Pb to 1200 K = 37. where Hpb(s). de represents the variation of HpbO(s) with temperature 298 ..298 = AH(a -+ f) + AH(f -+ g) + AH(g -+ d) + f 298 T cp. data for this system are listed in Table 6. T'. temperature.3000 the variation where H~02(g) is given as f2~8Cp.3.. Thus AHpbO. Pb(s) cp. d represents the enthalpy of I mole of PbO(s) at 298 K = AHpbO(S).000 + 1: in the range Cp. 6.. T = = -219.6 + 9.PbO(s) Cp. Pb = 32..9 + 26.. a represents the enthalpy of ~ mole of oxygen gas and 1 mole of Pb(s) at 298 K = (by convention).000 cp..mole from T m. Ph.HEAT CAPACITY.

7(T-298)+ -0.2~8) = -217. 02(g) 1 From the data in Table 6..130 METALLURGICAL THERMODYNAMICS and hence where !::. Pb(s) . -214 "0 E ~ -218 .9b For T = 500 K this gives tilisoo and 6.85 X 105 r+.96 + 10-3 T + 0.000 + iT 298 (-0.Cp = -0.96 X 10-3 T + 0. Pb). as can be seen in Figs.Cp = Cp. The variation with temperature of the enthalpy change for the reaction Pb + ~02 = PbO.3. PbO(s) =c». 6.10. -216 I I I I ----------+---------------I I ·0 .2 cp. dT 7.10. .85 X 105 (f .7 + 14.0 ~ <I -220 -222 200 400 600 T.K __ 800 1000 1200 Fig.800 joules. in the temperature range 298 to 600 K (T m. 6.85 X 105 T-2 and hence.000-0. tiliT = -219. !::.48 X 1O-3(T2 -2982) =-219.7 + 14.

hi represents the variation of the enthalpy of 1 mole of Pb(!) with temperature in the range of 600 K to 1200 K. In Fig. Pb hb is the latent heat of melting of Pb at the melting temperature of 600 K = 4810 joules. Hpb(l). ENTHALPY. which is given as Hpb(l)' 600 = J298 (600 Cp.PbO(s)dT Tm.Pb T' 298 cp PbO(s)dT . Cp.9b.Pb . and hence MiT' is calculated from the cycle.9a. ajkl represents the variation of the enthalpy of 1 mole of Pb and ~ mole of O2 (g). Pb = 4810 joules Mi(l-* e) = MiT' Mi(e -* g) = = Mi(g-*d) I f Tm. h represents the enthalpy of 1 mole of the Pb(!) at the melting temperature of o 600 K. 6. 6. then the latent heats of the phase changes must be considered. Pb(l)dT (T In Fig. Pb(s)dT+ Mim. Pb + J600 Cp. Mi298 = Mi(a -* d) = Mi(a -* j) + Mi(j -* k) + Mi(k + Mi(l-* e) -*!) + Mi(e -* g) + Mi(g -*d) where Mi(j -* k) = the latent heat of melting of Pb at Tm. between the two temperatures at which the reaction is being considered. T = J298 (600 Cp. ENTROPY AND THE THIRD LAW 131 If a phase change occurs in one or more of the reactants or products. Pb(s)dT + Mim.HEAT CAPACITY.

This reaction is the solid melting with an absorption of heat. solid and liquid coexisting at the melting point. 600 PbO (s) - Pb (I) ~ Cp.85 For T' = 1000 K.Mm. 6. If the temperature of interest is greater than both the melting temperature of the metal and the oxide. then the introduction of heat into this system (the external influence) results in the system's undergoing a reaction which tends to nullify the effect of the introduction of heat.. this gives MIOOO = -216. For example.5 +27. for .10 shows the variation of MpbO.to a high-temperature phase is always endothermic.700 joules as can be seen from Figs. e. PbO(s) =c«.Pb (-0.85 X 105r2)dT X 105r2)dT i: 600 (-9. MT' = M298 + .132 METALLURGICAL THERMODYNAMICS Thus. is subjected to the effects of an external influence.g. the system moves in that direction which tends to nullify the effects of the external influence. 6. which is drawn for the general oxidation reaction M + 1602 = MO. and the absorption of heat (the latent heat of the phase change) thus nullifies the effect of the addition of heat (which is the raising of the temperature) and the phase change occurs isothermally. Figure 6. then both latent heats of melting must be considered. care must be exercised with the signs of the heats of the phase changes." Thus if the system is a low-temperature phase in equilibrium with a high-temperature phase at the equilibrium phase-transition temperature.T with temperature in the range 298 to 1100 K. The signs can be obtained from a consideration of Le Chatelier's principle.9b and 6. with respect to Fig. 02(g))dT O2 (g))dT Ph + -219. A phase change from a low.96 X 10-3 T + 0. 298 Pb (Cp. - 2: - 1 Cp. Tm.000 + -4810+ 1 1 T' 298 (Cg.7 + 14. which states that "when a system.11. which is at equilibrium.10. = l Tm. Pb(s) Cp.8 X 1O-3T+0. and hence M for the change is always a positive quantity. When phase changes are to be considered.

11.MO __ change of a reaction. for the constant-pressure change of state. ENTHALPY. is always positive. The general Eq.9) can be obtained as For the state 1 For the state 2 Subtraction 1 -+ 2. The effect of phase changes on the enthalpy example. follows. . (6.M Temperature T Fig. ENTROPY AND THE THIRD LAW 133 t Q_ > 0 (ij I s: c ill ~ ~H298 l - 1 - I ----I-- \ I I I I I \ 1 298 Mfm MO(s) I I I I I I I I Tm. of these equations gives. 6. Tm.HEAT CAPACITY.

is obtained as (6.8) If the reversible process is conducted at constant pressure.cp dT (6. I:!.S is obtained as the area under the curve of either of the following: 1. for a closed system undergoing a reversible process.5 TEMPERATURE DEPENDENCE OF ENTROPY AND THE THIRD LAW OF THERMODYNAMICS From the Second Law.l2) For this change of state.13) . 6. then dS = (9_q_) T = (dH) p T p = cp dT T and thus if the temperature of a closed system of fixed composition is increased from T.S.l1) are expressions of Kirchhoff's law.11 ) Equations (6. cp versus In T between the limits In T2 and In T. to T2 at constant pressure. is given as (6.10) and (6. then the increase in the entropy per mole of the system. I:!. ST.134 or METALLURGICAL TH. = J'1 (T.10) and integrating between the states 1 and 2 gives !:iliT -!:iliT z 'T. dS= 8q T (3. Generally. cp/T versus T between the limits T2 and 2. I:!.ERMODYNAMICS (6. r. the entropy per mole of the system at any temperature T.

HEAT CAPACITY.2) with respect to T at constant P..g. This can be seen analytically by differentiation of Eq. ENTROPY AND THE THIRD LAW 135 where So is the entropy of the system per mole of the system at 0 K. Eq. for chemical reactions between pure solids or liquids.12. ENTHALPY. the slope of the line equals . Consideration of the numerical value of So leads to the enunciation of what is commonly termed the Third Law of Thermodynamics.12.S\ _ f1S sr sr aT~ t L1G oK T __ as the temperature Fig. For a change of state of a system. DJ{T. 6. (af1G) p = (~DJ{ \Jp _ T(at:. The variation of L1G with temperature approaches absolute zero. at the constant temperature T. the slope of the line approaches zero and the variation of the tangential intercept with temperature approaches zero.6. e. as T -+ 0. (5.12 at any temperature T. a chemical reaction. . In 1906 Nernst postulated that. then f1S -+ 0 and f1cp -+ O. In Fig.2) gives and thus Nernst's postulate was that f1G for the reaction varies with T as is shown in Fig. and the intercept of the tangent to the line at T with the T = 0 axis equals As the temperature approaches zero. (5. both the terms (af1G) aT p and approach zero as the temperature approaches absolute zero. the consequences of which are that.f1ST. 6.

" Thus for the general reaction A + B = AB = S AB . 1. the liquid. and a glass.s . which is in complete internal equilibrium.s) aT p = !:::." The requirement that the condensed phase be in complete internal equilibrium can be illustrated as follows. or freezing.12) (MG\ J =-!:::.S and !:::. the latent heat and entropy of crystallization at the temperature at which devitrification occurred.SA . and if SA and SB are assigned the value of zero at 0 K. and these liquids would require extensive atomic reorganization in order to assume the regular periodic structure characteristic of the crystalline state. not being in complete internal equilibrium.G/aT)p and (a!:::J!/aT)p tend to zero as T --* 0. simply becomes increasingly viscous and eventually forms a solid glass. internal energy. In the absence of the ability of the glass-forming substance to undergo the necessary atomic rearrangement at a unique thermodynamic crystallization. who enunciated that "the entropy of any homogeneous substance. the decreases in the enthalpy and entropy would be. Substances which form glasses normally have complex atomic.SB = 0 when T = 0 K. its enthalpy. then the compound AB also has zero entropy at 0 K.136 METALLURGICAL THERMODYNAMICS From Eq. Glasses are noncrystalline solids which are properly regarded as being supercooled liquids in which the liquidlike disordered atomic arrangement has been "frozen into" the solid state. (5. ionic.S sr p and hence (a!:::J!) p aT= T (a!:::. The Nernst heat theorem states that "for all reactions involving substances in the condensed state!:::.S is zero at the absolute zero of temperature. has an entropy at 0 K which is greater than zero by an amount which is dependent on the degree of atomic disorder in the glass. the glassy state is thus metastable with respect to the crystalline state.cp Thus if (a!:::. temperature.S/aT)p is not infinite at T = 0]. The incompleteness of Nernst's statement was pointed out by Planck. on cooling. or molecular structures in the liquid state. may be taken at zero at 0 K. Below the equilibrium thermodynamic freezing point. If the solid glass were to crystallize. then !:::.cp tend to zero as T--* 0 [provided that (a!:::. respectively. and entropy would decrease. !:::.

in the case of an alloy containing 50 atomic percent of A and 50 atomic percent of B.g. Again.HEAT CAPACITY. the maintenance of internal equilibrium becomes increasingly difficult. Solutions are mixtures of atoms. solid chlorine at 0 K is a solid solution of Cl3s _CI3s. 4. (4. and because of the chemical similarity between isotopes it would be expected that completely random mixing of the isotopes would occur. However as this entropy of mixing is present in any other substance which contains the element. giving rise. or molecules. the maintenance of the equilibrium degree of order is dependent on the ability of the particles to change their positions in the solution. Random crystallographic orientation of molecules in the crystalline state can also give rise to a nonzero entropy at 0 K. However. and a contribution is made to their entropy by the fact that they are mixtures [see Eq. with ever-decreasing temperature. For example. Even chemically pure elements are. Cps _CI37. 3. The equilibrium degree of order is temperature-dependent and increases as the temperature is decreased. it is customary to ignore it. 50 percent of its neighbors as A atoms and 50 percent as B atoms. At any temperature a pure crystalline solid contains an equilibrium number of point defects. ions. Such is the case with solid CO. e. the degrees of order in these two configurations would be unity and zero. Thus an entropy of mixing results and so. The atomic randomness of a mixture determines its degree of order. on the average.17)] . complete order would correspond to every A atom being surrounded only by B atoms and vice versa. in a strict sense.g. the entropy of such an element will not fall to zero at 0 K. This decrease is effected by the vacancies diffusing to the surface of the crystal where they disappear. where a solid structure such as CO OC OC OC CO OC CO CO CO OC OC CO OC CO OC OC OC . this number of defects must decrease as the temperature is decreased. thus. as atomic mobility decreases exponentially with decreasing temperature. as diffusivity decreases with decreasing temperature. in which case the entropy will not fall to zero at 0 K. a nonequilibrium concentration of defects can be frozen into the crystal.. ENTROPY AND THE THIRD LAW 137 2. and Cl37_Cp7 molecules. Consequently a none quilibrium degree of order can be frozen into the solid solution. give rise to an entropy of mixing which is exactly the same as the entropy of mixing in a chemical solution. mixtures of isotopes.. as a result of their random positioning in the crystal. e. ENTHALPY. in fact. and complete randomness would correspond to each atom having. This contribution is called the entropy of mixing and is determined by the randomness with which the component particles are mixed in the solution. to a nonzero entropy at 0 K. vacant lattice sites which. For internal equilibrium to be maintained. Respectively. and.

38054 X 20-23 X 4.SlV = 0.76 joules/degree. !::.mole In comparison with the measured entropy of 4.Sconf = = = k [(1 In Cf . e. at which the 0: and {3 phases are in equilibrium with each other. 6.g. !::.2 joules/degree-mole. and. 6. via Stirling's approximation. (4.~ d ln (~ Cf) . 0:={3 where 0: and {3 are solid allotropes of the element. the statement of the Third Law of Thermodynamics requires the inclusion of the qualification that the homogeneous phase be in complete internal equilibrium.S con ((n! In ---(~Cf)!(~Cf)! where (f is Avogadro's Number.0232 X 1023 per mole. as entropy is a state property. and hence .6 EXPERIMENTAL VERIFICATION OF THE THIRD LAW The Third Law can be experimentally tested by examining the behavior of some simple phase transition of an element.. be f=k !::. The maximum entropy would occur if equal numbers of molecules were oriented in opposite directions and random mixing of the two orientations occurred. 6. then for the cycle shown in Fig.13 Ttrans is the temperature.17). Thus. In Fig.138 METALLURGICAL THERMODYNAMICS can occur. For the Third Law to be obeyed. the configurational entropy of mixing would then.13. Per mole. at unit pressure.~ (j In (~ l1')] k X 4. 6. this indicates that the actual molecular orientations are not fully random.175 X 1023 1.175 X 1023 = 5. from Eq. As a result of the above considerations.

13. From these dependencies it was found that flSI =0 f 368. t {3 verification of the Third where flS and . ENTHALPY. a monoclinic form which is stable above 368. ENTROPY AND THE THIRD LAW 139 Ttrans -- ASI11 OK_ t Fig.5 K and a rhombohedral form which is stable below 368. which has two solid allotropes. 6.86 joules/degree ." These are equal if the Third Law is obeyed.t:Jf trans I! . As monoclinic sulfur can be supercooled with relative ease. Illustration of the experimental Law of Thermodynamics. with the latent heat of transformation being 400 joules/mole at 368.HEAT CAPACITY. 6.Ttrans MI! is termed the "experimental entropy change.5 K.5 K.13 has been examined for the case of sulfur.5 Cp(rhombic)dln T = 36. the temperature dependence of the heat capacities of both allotropes can be determined experimentally." and -(IlSI + MIll) is termed the "Third Law entropy change. The cycle shown in Fig.

368.810 932 1336 1356 1808 600 C(gr) C(diam) O2 .09 joules/degree As the difference between the experimental and the Third Law entropy changes is less than the experimental error.4 Element Al Au Cu Fe Pb S29.800 13. Assigning a zero value to So allows the absolute entropy of any pure substance to be determined as ST = iT o cpd In T joules/degree and molar entropies are normally tabulated at 298 K. e.3 47.3 27.694 2.800 4. the Table 6.44 205 joules AHm Tm K joules/degree 11. 6.02 flSm 10.8 joules/degree -{tSJ + tSnr) = -(36.500 12. joules/degree 28.8) = +0. this is taken as experimental verification of the Third Law. The variations of ST with temperature are illustrated in Fig.5 = . where S298 = 10 e 98 cpd In T joules/degree The values of S298 for a number of elements are listed in Table 6.14.3 9.94 joules/degree and MIl = +1.000 13..140 METALLURGICAL THERMODYNAMICS tSn = Ml trans Ttrans = 400 368.9 5.86 .5 Cp (monoclinicj-I In T = -37.37. 1.09 Joules/degree tSm = Thus 10 .63 8.59 7. Over the temperature range between 298 K and the temperature of the lowest phase change.58 9.2 64.g.36 33.4 along with the heats and temperatures of phase transition of the elements.

The molar entropies of several elements. with cp ST = S298 +Jr cpd 298 T .>:~ /' / ~fe\"t) Cu(s) 4) ~ ..~ C()2 - 2. __. ENTROPY AND THE THIRD LAW 141 260 240 220 200 180 160 (5 __. Al.. 6..K _ 400 Fig.14. gives In T = a + bT + cr2 = S298 + a In(2~8) + bt'I' - 298). melting temperature in the cases of Au. '" '" :g :. ENTHALPY.2. 70 ~ g UJ >c. and Cu. '" en' Auls) . is obtained as Mfm/T m : . and the ex ~ (3 transition in the case of Fe. 'te) C\g~ f' ~ ~ o 200 = »> -:.::.HEAT CAPACITY.v600 800 V f..----- --1400 1600 1800 2000 ~ 1000 1200 T.8 2) In the temperature range over which the liquid state exists. ST is obtained as ST which.. where llSm' the entropy of melting. c 60 50 r40 30 20 10 -: V ~ ~~AI(S) Fe(a) ~. ~c--- ~ --Au(I) ___ '" E 100 90 80 '" S.--C(diamond) ~f.

. which shows a plot of !:JIm versus Tm for a number of metals. . which states that !:JIm Tm -- = /:. Again the points lie close to a straight line with a slope of 88 joules/degree.Sm ~ 8 to 16 joules/degree Similarly Fig.15.15..142 METALLURGICAL THERMODYNAMICS Figure 6. K -- Illustration of Richards' rule. and this correlation is known as Trouton's rule which states that !:JI -r.16 shows a plot of !:JIp (the molar heat of evaporation at the boiling temperature. 200 400 600 800 1000 1200 1400 1600 1800 2000 Tm.. = /:. This correlation is known as Richards' rule.Sb p = 88 joules/degree Cr o o Fig. T b) versus Tb. 6. indicates that !:JIm/T m lies in the vicinity of 9 joules/degree. 6.

000 0 0 (") <j" zo 0 0 0 (") o o en N D0 .o \ O 0 0 N t ::<: _Q f- 0 0 en o o o o o en o 143 .

... J: C> "0: 0 0 0 L!l ~ 0 . ...0 8 L!l 0 0 0 .S E ~ o L!l M 00000 o M C'J L!l 0 C'J L!l 0 o L!l -.(j)o o o M "'" o o o M o o L!l C'J 0 \ 0 0 0 C'J t ~ I- .c.. ~ 143 alow/r>i 'ilHV' 'UO!lIlJodllila jo lllaH . 0 0: E-< "-< ... "3 . ..c. -.

6. 120 Kl g LU >. The variation with temperature of the entropy change for the reaction Pb + ~02 = PbO.144 METALLURGICAL THERMODYNAMICS It thus appears that the entropy of melting is approximately the same for all metals and the entropy of boiling is approximately the same for all metals.17. Figure 6.9. c 100 80 300 400 500 600 700 800 900 1000 1100 Temperature. K Fig.17 is the entropy-temperature diagram for the reaction Pb + ~02 = PbO corresponding to the enthalpy-temperature diagram shown in Fig. Generally Trouton's rule is more applicable than is Richards' rule. 6. and it is often used to estimate the value of Mlv for a substance from a knowledge of the boiling temperature of the liquid. a. 140 ~ . In view of the similar magnitudes of the molar entropies of the condensed phases Pb and 240 220 200 180 Q) "0 E Q) Q) Q) 160 S. .£ vi :.

This approximation is generally valid. ENTROPY AND THE THIRD LAW 145 PbO.10) gives dH = T dS + V dP. at 298 K. the entropy change is essentially that corresponding to the disappearance of the gas. 6. being given as I::lST = ST. .7 ENTHALPY AND ENTROPY AS FUNCTIONS OF PRESSURE For a closed system of fixed composition undergoing a change of pressure at constan t temperature.02 is very nearly equal to -1ST.9 .. i. dH= (aH) dP ap T Equation (5. = S298 PbO - S298 ' Pb -- 1 -2 S298 . is defined as a = of thermal expansion (aH) T =-TaV+ ap = V(1-aT) V .34) gives (as/ap)T =- (a v/aT)p. 0 2 = 67.HEAT CAPACITY.~ X 205 = -100 joules/degree which is very nearly equal to the entropy decrease resulting from the disappearance of half a mole of oxygen gas.e.64. for example. and thus Maxwell's relation (5. in reactions in which a gas reacts with a condensed phase to produce a condensed phase.02 1::lS298 . ENTHALPY. it is seen that the entropy change for the oxidation. in which case Gi)T = As the isobaric coefficient 1/ V(a v/aT)p. then T(~f)p + V a.4 . Pb - ~ST. PbO - ST.

14) For an ideal gas. 2 R IP In P = - R In (P2) p. for the change of state (PI. T) to (P2. Eq. with VAl = 1 ern" and CiAI = 0. and hence Eq.T) to (P2 . For a closed system of fixed composition undergoing a change of pressure at constant temperature.7. .15) For an ideal gas.T).1 ern" and the expansivity to be 0. =- R In (VI) V 2 as was obtained in Sec.69 X 10-4 (K)" I .l5) simplifies to l!. with Ci = liT. the same pressure increase at 298 K raises the molar enthalpy by 99.34). and assuming both of these to be virtually independent of pressure.S = --. (5. dS = (as) ap T dP From Maxwell's relation. gives 71 joules as the increase in the molar enthalpy of iron resulting from an increase in pressure from 1 to 100 atm at 298 K. Eq. Ci = liT. Similarly for aluminum.2 joules and this equals the increase in HAl obtained by heating from 298 to 302 Kat 1 atm pressure. (6.l4) again demonstrates that the enthalpy of an ideal gas is independent of pressure.3 X 10-4 (Ktl.146 METALLURGICAL THERMODYNAMICS and hence for the change of state (PI . T). (6. (6. 3. (6. and as then Ci=V 1 (av) aT p (as) ap = -CiV T Hence.P. The same enthalpy increase would be obtained by heating iron from 298 to 301 Kat 1 atm pressure. Taking the molar volume of iron to be 7.

where the range of pressure is normally from 0 to 1 atm.e.13).27 and 0.16) and combination of Eqs. ENTHALPY. ENTROPY AND THE THIRD LAW 147 In the case of iron at 298 K. In practice the heat-capacity and heat-of-formation data used in such calculations are experimentally determined by calorimetric methods.007 j oules/ degree. (6. from 298 K at 1 atm pressure. this is particularly so. However. both of these pressure dependencies can usually be ignored. i.1) and (6.1) and (6.12) and (6. then any substance in any thermodynamic state has a calculable absolute entropy.8 SUMMARY In this chapter it has been seen that knowledge of the heat capacities of substances and the heats of formation of compounds allows enthalpy and entropy changes to be evaluated for any process.HEAT CAPACITY. for phase changes and chemical reactions. (6. the pressure dependency of Hand S of substances occurring in condensed phases is normally small enough to be neglected in most applications (which involve pressure variation in the range of 0 to 1 atm). strictly.0022 joules/degree. (6.17) Just as it was required that the temperature dependence of cp be known for integration of Eqs. Although both enthalpy and entropy are dependent on pressure and temperature. In metallurgical applications.15) gives (6. an increase in the pressure from 1 to 100 atm decreases the molar entropy by 0. respectively. These decreases would be obtained by lowering the temperatures of Fe and AI by 0.14) gives (6.. but as the entropy of all substances (which are in complete internal equilibrium) at 0 K is zero. thus. combination of Eqs. For a closed system of fixed composition undergoing both temperature and pressure changes.09 degrees.15). that the molar enthalpies and entropies of condensed phases are relatively insensitive to pressure change. 6. and for aluminum the corresponding decrease is 0. It is seen. for condensed phases being considered over small ranges of pressure. . In dealing with enthalpy it is conventional to assign the value of zero to the enthalpy of elements in their stable state of existence at 298 K. it is required that the pressure dependence of V and a be known for integration of Eqs. (6.14) and (6.

Feb ~ ~ ~ ~ Mitrans Mitrans Mitrans Mim = 5020 920 880 13. on completion of the reaction. An examination of this is started in Chap.5 X lOsr-2 joules/degree-mole = -1. 6.000 = = 106. isobaric process provides the criterion of reaction equilibrium.5 X 10-3 Tjoules/degree'mole from 1181 = 43.300 joules/mole joules/mole X 1O-3T-28.5 + 24.9 joules/degree-mole from 1674 to 1808 K = 41.03) Cp(Al.674. calculate the molar ratio of Fe to Fe203 in the initial mixture which. 03 + 2Fe) is allowed to proceed to completion. will give liquid Fe and solid Al203 at 1600°C.6 + 17.8 in the temperature range 298-1873 K Cp(Fea) C (Fe{3) p cp(Fe'Y) cp(Feo) Cp(Fel) 17.8 X 10-3 Tjoules/degree'mo1e from 273 to 1033 K = 38 joules/degree-mole from 1033 to 1181 K = 7. Given: H298(Fe.800 joules/mole joules/mole joules/mole joules/mole . is adiabatically contained along with some Fe at 25°C.03) H298(Al. present in the molar ratio 1:2. Feb FeZ joules/degree-mole = to 1674 K from 1808 to 1873 K at at at at Ttrans Ttrans Ttrans Tm 1033 1181 1674 1808 K K K K For For For For Peo Fe~ Fe/.ST for any reaction at any temperature (and pressure) allows the all-important Gibbs free energy change for the reaction to be calculated as As consideration of the Gibbs free energy in any isothermal.9 NUMERICAL EXAMPLES Example 1 A mixture of Fe203 and AI.8 Fe~ Fe/. If the Thermit reaction (Fe203 + 2AI = Al.0 3 ) = -821. 7. it is seen that the equilibrium state of a reaction system can be determined from a knowledge of the thermochemical properties of the components of the system.148 METALLURGICAL THERMODYNAMICS The determination of MiT and t.7 + 19.

1873 Ml2 =[ 298 Cp(AI 2 0 )dT 3 = 106. Thus the temperature of the point c is determined by the value of n.298) + 24. -Ha the heat to raise the temperature of (n + 2) moles of Fe from 298 to 1873 K (Mil) + the heat to raise the temperature of 1 mole of A1203 from 298 to 1873 K (Ml2). 6.8 X 10-3(18732 -2982) . (2 + n)Fe + Al203 at 298°K ~ (2 + n)Fe + Al203 at 1873 K where n is the number of moles of Fe present in the initial mixture per mole of Fe2 03. In Fig. For the Thermit reaction at 298 K Fe203 + 2AI Ml298 Mill = Ah03 + 2Fe joules = -1.2982) (n + 2)' 2 + 5020 + 38 X (1181 .6(1873 -298) + 28. ENTHALPY.5 X 10-3(16742 -11812) + 880+ 43. As the system is adiabatically contained.5 X lOs C8\3 + 1~.1808) = 77.7(1674-1181)+ 1~.300 = -852. I.1674) + 13.18 the slope of each individual segment of the line be is (n + 2)cp(Fe) + cp(AI203)' and the length of each vertical segment equals (n + 2)MlFe(trans).1033) + 920 +7.674.800 + 41.8 X (1873 .2!8) 190.8 X 10-3(10332 .HEAT CAPACITY. ENTROPY AND THE THIRD LAW 149 Consider the system per mole of Fe2 03 and consider the process path.700 = Mil =Hi. Fe203 + 2AI ~ 2Fe + Al2 03 at 298 K.000 = + 821.300 joules = Mil = 175(1033 . Mil + Mill = O.360 joules Thus .9 X (1808 . followed by II.

56 moles of Fe per mole of Fe2 03 initially present.5 + 26 X 1O-3Tjoulesjdegree mole The equilibrium state of the adiabatically contained system is that in which solid. and as the process is adiabatic the enthalpy of the system remains constant.2 XlO-3Tjoulesjdegree mole o = 18.Sn(l) cp.e. Given: b.7 -9. 6. which has spontaneously formed.360n + 154. and the remaining liquid coexist at 505 K. Thus the fraction of liquid which freezes is of such magnitude as to release the heat necessary to raise the temperature of the system from 495 to 505 K. i.19 the process is represented by the change of state from a to c. Example 2 A quantity of supercooled liquid tin is adiabatically contained Calculate the fraction of tin which spontaneously freezes.720 + 190. Let the molar fraction which freezes equal x and consider 1 mole of the system. = 7070joulesjmole = at Tm = 505 K o 34..Sn(s) at 495 K.Hm(Sn) cp. 6.18. .700 or n = 77.150 METALLURGICAL THERMODYNAMICS o a c t H b 298 1033 T _ 1 81 1674 1808 1873 Fig. 852.300 = 6. In Fig.

_----_-----' d t x moles solid (1 .. In this case...505) . Sn(l)dT= 34...26 percent of the tin freezes....... i. and then the fraction x freezes at 505 K....cp(s . and then the temperature of the solid formed and remaining liquid is increased from 495 to 505 K.2 X 10-3(4952 - 5052) 7084 joules/mole c .19.e..t:J-l(d . all of the liquid is increased in temperature from 495 to 505 K. c) = -7070x = 7070 301 = joules 0.. 495 K _ t a . on a molar basis 4. the fraction x freezes at 495 K. 6... C) t:J-l(a d) = the heat of freezing of x moles of tin at 495 K K) = -xt:J-lm(495 But t:J-lm(495 K) = t:J-lm(505 K) + 1 495 50S 6.x) moles liquid 1 mole liquid Fig.. a ~ d ~ c.0426 and so x i. a ~ b ~ c.9:/ X 10-3(5052 - 4952) = 301 joules t:J-l(b .e. i.... ENTROPY AND THE THIRD LAW 151 Two paths can be conveniently considered: Path I.. t:J-l(a t:J-l(a b) =- b) = L:: t:J-l(b ...3~...------l_-----.e.7(505 .2(495 = 505 K _ b ... . In this case t:J-l(a d) = . c) 5 cp.495) . Path II. dT 1) = 7070 + 16. ENTHALPY.HEAT CAPACITY.

the process of freezing and temperature increase will occur simultaneously. molar entropy. Calculate the weight of Cr203 which.4952 [34.0426 The actual path followed by the process will be intermediate between paths 1 and II.e. PROBLEMS Thermodynamic 6.5(505 .3 Calculate the difference in molar enthalpy. X 10-\5052 )J -4952~ + (I-x) =301+14x Thus and so -7084x = -14x x . Cr(s)' and Cr203(S) to 1000°C.. i. .4 An adiabatic vessel contains 1000 grams of liquid aluminum at 700°C. Necessary for the Solution of These Problems. and molar free energy between liquid and solid bismuth at 800 K. The initial temperature of the added Cr2 03 is 2SoC.495) + 22 X 10-3(5052 .7(505 -495)_9:. when added to the liquid aluminum (with which it reacts to form Cr and Al2 03) raises the temperature of the resulting mixture of AI203(s).1 Data. is Tabulated in the Appendix and tlSlOOO for the reaction Calculate M/lOOO 6.152 METALLURGICAL THERMODYNAMICS Thus M/(a-+d) = -7084x joules M/(d-+c)=x 1 495 505 cp(s)dT+(1-x) 1505 cp(l)dT 495 = x[ 6 18.301 = 301 7070 = 0. Which of the following processes releases more heat? (i) Oxidation of graphite to CO at 1000 K (ii) Oxidation of diamond to CO at 1000 K 6.2 6.

the final temperature is 80°C. T = 273 K).98 and cp . and when the initial temperature of the aluminum is 359°C.8 A calorimeter of water-equivalent 20 grams contains 100 grams of water at 25°C. ENTROPY AND THE THIRD LAW 153 6. and AS298 for the reactions: (a) 4VO(s) (b) 2V203(S) (c) 4V02(s) + O2 (g) = 2V203(S) + O2 (g) = 4V02(s) + O2 (g) = 2'{205 (s) . the coefficient of cubical expansion of Au is 4.5 K-1. t::J-f298. are listed below. Calculate t::J-f298 and AG298 for the reaction 4CaO + Si = 2Ca + Ca2 Si04 6.44 joules/degree in the + ! 2 (g) = O MnO(s) 6. When the initial temperature of the aluminum is 243°C. When a l Ou-gram mass of aluminum at 121°C is placed in the calorimeter. From this information calculate AG298. Calculate t::J-f 1800for the reaction Mn(l) 75.10 The molar heats of formation and entropies of formation at 298 K. of various vanadium oxides from vanadium metal and oxygen gas.6 6.HEAT CAPACITY.30 grams/em". and the atomic weight of Au is 197.9 The atomic weight of Al is 26.7 How much error is involved if it is assumed that ACp for this reaction is zero? One mole of gold is taken from state 1 (P = 1 atm. T = 293 K) to state 2 (P = 1 atm. the final temperature in the calorimeter is 60°C. From this data determine the molar heat capacity of aluminum in the form cp = a + bT = 6. ENTHALPY. What pressure must be applied to the gold at 273 K in order to raise its enthalpy back to that of state 1 (call this state 3)? Calculate the entropy difference between states 1 and 3. which is independent of pressure. H 2 0 temperature range 273 to 373 K. Given: the density of Au at 20°C is 19. the final temperature at 40°C.32 X 10.5 Calculate the value of AG600 for the reaction NiO(s) + CO(s) = CoO(s) + Ni(s) 6.

V.05 -431.03 VO.8 -1550 I -92.mole of oxide VO V.5 -358 -184 -441 .154 METALLURGICAL THERMODYNAMICS Oxide All'98 kJ/mole of oxide AS'98 joules/degree.8 -1219 -713.

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