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D6.1

Phase diagrams

Phase: a state of matter that is uniform throughout, not only in chemical composition but also in physical state. Constituent: any chemical species present in the system. Component: a chemically independent constituent of the system. It is best understood in relation to the phrase number of components which is the minimum number of independent species necessary to dene the composition of all the phases present in the system. Degree of freedom (or variance): the number of intensive variables that can be changed without disturbing the number of phases in equilibrium.

D6.3

Figure 6.1(a)

118

SOLUTIONS MANUAL

Figure 6.1(b)

D6.3

Figure 6.2

Solutions to exercises

E6.1(a)

An expression for composition of the solution in terms of its vapor pressure is required. This is obtained from Daltons law and Raoults law as follows

p = pA + pB [Daltons law] = xA p A + (1 xA )pB .

Solving for xA , xA =

p p B . p A pB

PHASE DIAGRAMS

119

For boiling under 0.50 atm (50.7 kPa) pressure, the combined vapor pressure, p, must be 50.7 kPa; hence xA = 50.7 20.0 = 0.920 , xB = 0.080 . 53.3 20.0

The composition of the vapor is given by eqn 6.5, yA = xA p 0.920 53.3 A = = 0.968 pB + (pA pB )xA 20.0 + (53.3 20.0) 0.920 and

yB = 1 0.968 = 0.032 .

E6.2(a)

The vapor pressures of components A and B may be expressed in terms of both their composition in the vapor and in the liquid. The pressures are the same whatever the expression; hence the expressions can be set equal to each other and solved for the composition. pA = yA p = 0.350p = xA p A = xA (76.7 kPa), pB = yB p = (1 yA )p = 0.650p = xB p B = (1 xA ) 52.0 kPa). x A p yA p A . = yB p xB p B

Therefore, Hence

E6.3(a)

(a) Check to see if Raoults law holds; if it does the solution is ideal. p A = xA p A = (0.6589) (127.6 kPa) = 84.07 kPa, p B = xA p B = (0.3411) (50.60 kPa) = 17.26 kPa, p = pA + pB = 101.3 kPa = 1 atm. Since this is the pressure at which boiling occurs, Raoults law holds and the solution is ideal . pA 84.07 kPa yB = 1 yA = 1.000 0.830 = 0.170 . [6.4] = = 0.830 , (b) yA = p 101.3 kPa

E6.4(a)

(a)

p(total) = pDE + pDP [Daltons law] = xDE p DE + xDP pDP [Raoults law, 6.3].

xDE = zDE ,

p(total) = (0.60) (22.9 kPa) + (0.40) (17.1 kPa) = 13.7 + 6.8 = 20.5 k Pa . (b) yDE = pDE 13.7 kPa = 0.67 , [6.4] = p 20.5 kPa yDP = 1 yDE = 0.33 .

120

E6.5(a)

SOLUTIONS MANUAL

The data are plotted in Fig. 6.3. From the graph, the vapor in equilibrium with a liquid of composition (a) xM = 0.25 is determined from the tie line labeled a in the gure extending from xM = 0.25 to yM = 0.36 , (b) x0 = 0.25 is determined from the tie line labeled b in the gure extending from xM = 0.75 to yM = 0.82 .

Figure 6.3

E6.6(a)

(a) Though there are three constituents, salt, water, and water vapor, there is an equilibrium condition between liquid water and its vapor. Hence, C = 2 . (b) Disregarding the water vapor for the reasons in (a) there are seven species: Na+ , H+ , H2 PO 4, 3 HPO2 4 PO4 , H2 O, OH . There are also three equilibria, namely, H2 PO 4

HPO2 4 H+ + HPO2 4 , H+ + PO3 4 ,

H+ OH

H2 O.

(These could all be written as Brnsted equilibria without changing the conclusions.) There are also two conditions of electrical neutrality, namely, [Na+ ] = [phosphates], [H+ ] = [OH ] + [phosphates]

2 3 where [phosphates] = [H2 PO 4 ] + 2[HPO4 ] + 3[PO4 ]. Hence, the number of independent components is

C = 7 (3 + 2) = 2 .

E6.7(a)

There are two solids, but one solid phase, as well as a gaseous phase; hence P = 2 . Assuming all the water and CuSO4 are formed by the dehydration, their amounts are then xed by the equilibrium; hence C=2 .

E6.8(a)

(a) The two components are Na2 SO4 and H2 O (proton transfer equilibria to give HSO 4 , etc. do not change the number of independent components) so C = 2 . There are three phases present (solid salt, liquid solution, vapour), so P = 3 . (b) The variance is F = C P + 2 = 2 3 + 2 = 1 .

PHASE DIAGRAMS

121

Either pressure or temperature may be considered the independent variable, but not both as long as the equilibrium is maintained. If the pressure is changed, the temperature must be changed to maintain the equilibrium.

E6.9(a)

Figure 6.4 Refer to Fig. 6.26 of the text. At b3 there are two phases with compositions xA = 0.18 and xA = 0.70; their abundances are in the ratio 0.13 (lever rule). Since C = 2 and P = 2 we have F = 2 (such as p and x ). On heating, the phases merge, and the single-phase region is encountered. Then F = 3 (such as p, T , and x ). The liquid comes into equilibrium with its vapor when the isopleth cuts the phase line. At this temperature, and for all points up to b1 , C = 2 and P = 2, implying that F = 2 (for example p, x ). The whole sample is a vapor above b1 . The incongruent melting point (Section 6.6) is marked as T1 = 400 C in Fig. 6.5(a). The composition of the eutectic is marked as xe ( 0.30) in the gure. Its melting point is T2 ( 200 C). The cooling curves are shown in Fig. 6.5(b). Note the breaks (abrupt change in slope) at temperatures corresponding to points a1 , a2 , b1 , b2 . Also note the eutectic halt at b3 . Refer to Fig. 6.6. (a) The solubility of silver in tin at 800 C is determined by the point c1 (at higher proportions of silver, the system separates into two phases). The point c1 corresponds to 80 per cent silver by mass. (b) See point c2 . The compound Ag3 Sn decomposes at this temperature. (c) The solubility of Ag3 Sn in silver is given point c3 at 300 C.

E6.14(a)

E6.10(a)

E6.11(a)

E6.12(a)

E6.13(a)

(a) See Figs. 6.7(a) and (b). (b) Follow line b in Fig. 6.7(a) down to the liquid line which intersects at point b1 . The vapor pressure at b1 is 620 Torr .

122

SOLUTIONS MANUAL

Figure 6.5

Figure 6.6

(c) Follow line b in Fig. 6.7(a) down to the vapor line which intersects at point b2 . The vapor pressure at b2 is 490 Torr . From points b1 to b2 , the system changes from essentially all liquid to essentially all vapor. (d) Consider tie line d ; point b1 gives the mole fractions of the liquid, which are x (Hep) = 0.50 = 1 x (Hex), x (Hex) = 0.50 .

Point d1 gives the mole fractions in the vapor which are y(Hep) 0.28 = 1 y(Hex), y(Hex) 0.72 .

PHASE DIAGRAMS

123

Figure 6.7(a)

Figure 6.7(b)

(e) Consider tie line e; point b2 gives the mole fractions in the vapor, which are y(Hep) = 0.50 = 1 y(Hex), y(Hex) = 0.50 .

Point e1 gives the mole fractions in the liquid, which are x (Hep) = 0.70 = 1 x (Hex), x (Hex) = 0.30 .

(f) Consider tie line f . The section, ll , from point f1 to the liquid line gives the relative amount of vapor; the section, lv , from point f1 to the liquid line gives the relative amount of liquid. That is nv lv = nl ll [6.7] or nv ll 6 = . nl lv 1

124

E6.15(a)

SOLUTIONS MANUAL

Figure 6.8

E6.16(a)

The cooling curves are sketched in Fig. 6.9. Note the breaks and halts. The breaks correspond to changes in the rate of cooling due to the freezing out of a solid, which releases its heat of fusion and thus slows down the cooling process. The halts correspond to the existence of three phases and hence no variance until one of the phases disappears.

Figure 6.9

E6.17(a)

Figure 6.10

PHASE DIAGRAMS

125

(a) The mixture has a single liquid phase at all compositions. (b) When the composition reaches x (C6 F14 ) = 0.24 the mixture separates into two liquid phases of compositions x = 0.24 and 0.48. The relative amounts of the two phases change until the composition reaches x = 0.48. At all mole fractions greater than 0.48 in C6 F14 , the mixture forms a single liquid phase.

Solutions to problems

Solutions to numerical problems

P6.1

(a) The data, including that for pure chlorobenzene, are plotted in Fig. 6.11.

Figure 6.11 (b) The smooth curve through the x , T data crosses x = 0.300 at 391.0 K, the boiling point of the mixture. (c) We need not interpolate data, for 393.94 K is a temperature for which we have experimental data. The mole fraction of 1-butanol in the liquid phase is 0.1700 and in the vapor phase 0.3691. According to the lever rule, the proportions of the two phases are in an inverse ratio of the distances their mole fractions are from the composition point in question. That is, nliq v 0.3691 0.300 = = = 0.532 . nvap l 0.300 0.1700

P6.3

p A = aA p A = A xA pA [5.45].

A =

pA yA p = . xA p x A pA A

Sample calculation at 80 K: O2 (80 K ) = 0.11(100 kPa) 0.34(225 Torr) 760 Torr , 101.325 kPa

O2 (80 K ) = 1.079.

126

SOLUTIONS MANUAL

Summary: T /K O2 77.3 78 0.877 80 1.079 82 1.039 84 0.995 86 0.993 88 0.990 90.2 0.987

To within the experimental uncertainties the solution appears to be ideal ( = 1). The low value at 78 K may be caused by nonideality; however, the larger relative uncertainty in y(O2 ) is probably the origin of the low value. A temperaturecomposition diagram is shown in Fig. 6.12(a). The near ideality of this solution is, however, best shown in the pressurecomposition diagram of Fig. 6.12(b). The liquid line is essentially a straight line as predicted for an ideal solution.

Figure 6.12(a)

Figure 6.12(b)

PHASE DIAGRAMS

127

P6.5

A compound with probable formula A3 B exists. It melts incongruently at 700 C, undergoing the peritectic reaction A3 B(s) A(s) + (A + B, l). The proportions of A and B in the product are dependent upon the overall composition and the temperature. A eutectic exists at 400 C and xB 0.83. See Fig. 6.13.

Figure 6.13

P6.7

The information has been used to construct the phase diagram in Fig. 6.14(a). In MgCu2 the mass percent24.3 48.6 age of Mg is (100) 24.3 +127 = 16 , and in Mg2 Cu it is (100) 48.6+63.5 = 43 . The initial point is a1 , corresponding to a liquid single-phase system. At a2 (at 720 C) MgCu2 begins to come out of solution and the liquid becomes richer in Mg, moving toward e2 . At a3 there is solid MgCu2 + liquid of composition e2 (33 per cent by mass of Mg). This solution freezes without further change. The cooling curve will resemble that shown in Fig. 6.14(b).

(a) 1200 a

(b)

800 e1

a1 a2 a3 e2 e3

400

Figure 6.14

128

P6.9

SOLUTIONS MANUAL

(a)

Eutectic: 40.2 at % Si at 1268 C , Eutectic: 69.4 at % Si at 1030 C [6.6]. Congruent melting compounds: Ca2 Si mp = [6.7]. 1314 C CaSi mp = 1324 C Incongruent melting compound: CaSi2 mp = 1040 C melts into CaSi(s) and liquid (68 at %Si).

(b) At 1000 C the phases at equilibrium will be Ca(s) and liquid (13 at % Si) . The lever rule gives the relative amounts: lliq 0.2 0 nCa = = = 2.86 . lCa nliq 0.2 0.13 (c) When an 80 at% Si melt it cooled in a manner that maintains equilibrium, Si(s) begins to appear at about 1250 C. Further cooling causes more Si(s) to freeze out of the melt so that the melt becomes more concentrated in Ca. There is a 69.4 at% Si eutectic at 1030 C. Just before the eutectic is reached, the lever rule says that the relative amounts of the Si(s) and liquid (69.4% Si) phases are: lliq 0.80 0.694 nSi = = = 0.53 = relative amounts at T slightly higher than 1030 C . nliq lSi 1.0 0.80 Just before 10.30 C, the Si(s) is 34.6 mol% of the total heterogeneous mixture, the eutectic liquid is 65.4 mol%. At the eutectic temperature a third phase appearsCaSi2 (s). As the melt cools at this temperature, both Si(s) and CaSi2 (s) freeze out of the melt while the concentration of the melt remains constant. At a temperature slightly below 1030 C, all the melt will have frozen to Si(s) and CaSi2 (s) with the relative amounts: nSi nCaSi2 = lCaSi2 0.80 0.667 = lSi 1.0 0.80

= 0.665 = relative amounts of T slightly higher than 1030 C . Just under 1030 C, the Si(s) is 39.9 mol% of the total heterogeneous mixture; the CaSi2 (s) is 60.1 mol%. A graph of mol% Si(s) and mol% CaSi2 (s) vs. mol% eutectic liquid is a convenient way to show relative amounts of the three phases as the eutectic liquid freezes. See Fig. 6.15. Equations for the graph are derived with the law of conservation of mass. For the silicon mass, nzSi = nliq wSi + nSi xSi + nCaSi2 ySi where n = total number of moles. wSi = Si fraction in eutectic liquid = 0.694 xSi = Si fraction in Si(s) = 1.000 ySi = Si fraction in CaSi2 (s) = 0.667 ZSi = Si fraction in melt = 0.800

PHASE DIAGRAMS

129

This equation may be rewritten in mole fractions of each phase by dividing by n: zSi = (mol fraction liq)wSi + (mol fraction Si)xSi + (mol fraction CaSi2 )ySi . Since, (mol fraction liq) + (mol fraction Si) + (mol fraction CaSi2 ) = 1 or (mol fraction CaSi2 ) = 1 (mol fraction liq + mol fraction Si), we may write: zSi = (mol fraction liq)wSi + (mol fraction Si)xSi + [1 (mol fraction liq + mol fraction Si)]ySi . Solving for mol fraction Si: mol fraction Si := (zSi ySi ) (wSi ySi )(mol fraction liq) , xSi ySi

mol fraction CaSi2 := 1 (mol fraction liq + mol fraction Si). These two eqns are used to prepare plots of the mol fraction of Si and mol fraction of CaSi2 against the mol fraction of the melt in the range 00.65.

Freezing of eutectic melt at 1030C 0.7 0.6 0.5 0.4 mol fraction CaSi2 mol fraction Si 0.3 0.2 0.1 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Figure 6.15

P6.11

The general condition of equilibrium in an isolated system is dS = 0. Hence, if and constitute an isolated system, which are in thermal contact with each other dS = dS + dS = 0. (a)

130

SOLUTIONS MANUAL

The implication of this problem is that energy in the form of heat may be transferred from one phase to another, but that the phases are mechanically rigid, and hence their volumes are constant. Thus, dV = 0, and dS = S U d U +

V

S U

d U =

V

1 1 d U + dU [3.45]. T T

But, dU = dU ; therefore

1 1 = or T = T . T T

Solutions to applications

P6.13

(i) Below a denaturant concentration of 0.1 only the native and unfolded forms are stable. (ii) At denaturant concentration of 0.15 only the native form is stable below a temperature of about 0.70. At temperature 0.70 the native and molten-globule forms are at equilibrium. Heating above 0.70 causes all native forms to become molten-globules. At temperature 0.90, equilibrium between molten-globule and unfolded protein is observed and above this temperature only the unfolded form is stable. C = 1; hence, F = C P + 2 = 3 P.

P6.15

Since the tube is sealed there will always be some gaseous compound in equilibrium with the condensed phases. Thus when liquid begins to form upon melting, P = 3 (s, l, and g) and F = 0, corresponding to a denite melting temperature. At the transition to a normal liquid, P = 3(l , l , and g) as well, so again F = 0.

P6.17

To examine the process of zone levelling with the phase diagram below, Fig. 6.16, consider a solid on the isopleth through a1 and heat the sample without coming to overall equilibrium. If the temperature rises to a2 , a liquid of composition b2 forms and the remaining solid is at a2 . Heating that solid down an isopleth passing through a2 forms a liquid of composition b3 and leaves the solid at a3 . This sequence of heater passes shows that in a pass the impurities at the end of a sample are reduced while being transferred to the liquid phase which moves with the heater down the length of the sample. With enough passes the dopant, which is initially at the end of the sample, is distributed evenly throughout. The data are plotted in Fig. 6.17. (a) As the solid composition x (MgO) = 0.3 is heated, liquid begins to form when the solid (lower) line is reached at 2150 C . (b) From the tie line at 2200 C, the liquid composition is y(MgO) = 0.18 and the solid x (MgO) = 0.35 .

P6.19

PHASE DIAGRAMS

A liquid B

131

Temperature, T

a'3

a3

b3

a'2 solid

a2 a1 a

b2 b1

0 Composition, xB

Figure 6.16

Figure 6.17

Figure 6.18 The proportions of the two phases are given by the lever rule, l1 n(liq) 0.05 = = = 0.4 . l2 n(sol) 0.12 (c) Solidication begins at point c, corresponding to 2640 C .

132

P6.21

SOLUTIONS MANUAL

(a) The data are plotted in Fig. 6.18. (b) We need not interpolate data, for 6.02 MPa is a pressure for which we have experimental data. The mole fraction of CO2 in the liquid phase is 0.4541 and in the vapor phase 0.9980. The proportions of the two phases are in an inverse ratio of the distance their mole fractions are from the composition point in question, according to the lever rule nliq v 0.9980 0.5000 = = = 10.85 . nvap l 0.5000 0.4541

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