8 Phase Diagrams and the Relative Stability of solids,Liquids and Gases

Problema numbers in italies indicate that the solution is included in the student solutions manual.Conceptual
problems

Q8.1 Why is it reasonable to show the µ versus t segments for the three phases as straight
lines as is done in figure 8.1? More realistic curves would have some curvature. Is the
curvature upward or downward on a µ versus t plot? Explain your answer
𝜕𝜇
( ) = -S.Because S increases slowly with t, the realistie curves Will curve downward,
𝜕𝑡

But not very rapidly.

Q8.2 why do the temperature versus heat curves in the solid, liquid, and gas regions of Figure 8.7
have different slopes?
The slope of these curves are equal to the inverse of CÞ,m, which has different values for the
Thres phases as can be seen in Figure 2.9.
Q8.3 Figure 8.7 is not drawn tos cale. What would be the relative lengths on the qp axis of the liquid

Segment, the length is ∁ ∆𝑇 ; and for the liquid + gas segment, the length is ∆𝐻 vaporization
Numerically, for water, using table 8.2, the relative length are 6010 Jmol-1 , and 40650 Jmol-1.

Q8.4 Show the paths 𝑛 → 𝑜 → 𝑝 → 𝑞 𝑎𝑛𝑑 𝑎 → 𝑏 → 𝑐 → 𝑑 → 𝑒 → f 𝑜𝑓 𝑡ℎ𝑒 P-V-T plase diagramo of

Figure 8.15 in the P -T plase diagram of Figure 8.4

Q8.5 At a given temperatura, a liquid can coexist with its gas at a single value of the pressu-
re. However, you can sense the presence of H2(g) above the Surface of a lake by the
humidity, and it is still there if the barometric pressurerises or falls at constant tempe-
rature.How is thi possible?
The statement that at a given temperatura, a liquid can coexist with its gas at a single
Value of the pressure holds for a system with only one substance. For the case descri-
bed, the system consists of water and air. The change in barometric pressure is equiva-
lent to an external pressure exerted on a liquid. As discussed in section 8.7, this Will
 change the vapor pressure only slightly.
Q8.6 Why are the triple point temperatura and the normal freezing point very close in tem-
Perature for most substances? This is the case because the freezing point changes only
Slightly with pressure.
Q8.7 Give a molecular level explanation as to why the Surface tensión of Hg(l) is not zero.
Hg atoms have a strong attractive interaction. The atoms at the Surface of a droplet
Have fewer nearest neighbors tan an atom in the liquid. They experience a net force perpendi-
Cular to the Surface that Will lead to a pressure increase inside the droplet.

Q8.8 A vessel containing a liquid is opened inside an evacuated chamber. Will you see a liquid-gas
Interface if the volume of the initially evacuated chamber is(a) les tan the critical volume, (b) a
Factor of 10 larger than the critical volumen, and (c) a factor of 1.05 larger than the critical
Volume?
(a) No, because the liquid and gas are not distinguishable above the critical density.
(b) No, because all the liquid Will evaporate.
(c) Yes, because the density is less than the critical density.
Q8.9 why are there no points in the plase diagran for sulfur in figure 8.11 that show rhombic and
Monoclinic solid phases in equilibrium with liquid and gaseous sulfur?
Acoording to the Gibbs phase rule, four phases of a pure substance cannot coexist.
Q8.10 What is the physical origino f the pressure difference across a curved liquid-gas interface?
The origin is the cohesive forces in the liquid. Across an interface, the resultant force vector is
Not zero in magnitude. If the interface is curved, the resultant force tends to minimize the
Surface área, leading to a pressure difference across the interface.
Q8.11 A triple point refers to a point in a P-T phase diagram for whiththree phases are in equilibrium.
Do all triple points correspond to a gas-liquid-solid equilibrium?
No. If there are several solid phases, there can be a triple point corresponding to equilibrium
Among three solid phases.
Q8.12 Why does the liquid-gascoexistence curve in a P-T phase diagram end at the critical point?
At the critical point, the gas and liquid have the same density,and can no longer be
Distinguished. This is also true for all point on the liquid-gas coexistence curve extended beyond the critical
point.
Q8.13 How can you get a P-T phase diagram from a P-V-T phase diagram?
You get a P-T phase diagram from by projecting a P-V-T phase diagrama on the P-T plane.
Q8.14 Why does the triple point in a P-T diagram become a triple line in a P-V diagram?
This is the case because a gas and a liquid are in equilibrium for the range of values of volumen
From that of the pure liquid to that of the pure gas at a given temperatura.
Q8.15 Why does water have several different solid phases, but only one liquid and one gaseous phase?
Liquid and gaseous phase are disordered, so that except for special cases such as superfluid and
Normal He(l), there is no way to distinguish two different liquid or gaseous simples of the same
Pure substance.
Q8.16 As the pressure is increased at -45ºC, ice I is converted to ice II. Which of these phases has the
Lower density? The higher density phase is more stable as the pressure is increased, according
To lechatelier`s principle. Therefore ice I is the les dense phase.

Q8.17 why is ∆𝐻 sublimation=∆𝐻 fusión +∆ 𝐻 vaporization?

Because H is a state are function,∆𝐻has the same value for solid→ 𝑔𝑎𝑠 𝑜𝑟 𝑠𝑜𝑙𝑖𝑑 → 𝑙𝑖𝑞𝑢𝑖𝑑 →
Gas as long as the initial and final states are the same for these two processes.
Q8.18 Make a graph of the densities of a liquid and ist gas as a function of the temperature from low
Temperatures up to the critical point. Explain the behavior at the critical point.

Q8.19 What can you say about ∆𝐻 vaporization of a liquid as the temperature approaches the critical

Temperature? ∆𝐻 vaporización decreases slowly far from the critical temperature and rapidly as it
Approaches the critical temperature where it has the value zero.
Q8.20 Is the following statement corret? Because dry ice sublimes, carbon dioxide has no liquid phase
Explain your answer.
It is not correct. Carbon dioxide has a liquid phase above the triple point, but not at 298K.
Q821 Make a drawing indicating the four- step process d of figure 8.4

Numerical problems
P8.1 Use the vapor pressures of tetrachloromethane given in the following table to calculate
The enthalpy of vaporization using a graphical method or a least squares fitting routine.
T(K) P/Pa T(K) P/Pa
280 6440 320 37130
290 10540 330 53250
300 16580 340 74520
310 25190

P8.2 The vapor pressure of ethanol(l) is given by

𝑝 3.6745𝑥103
ln ( ) = 23.58 − 𝑇
𝑝𝑎 − 46.720
𝐾

a. Calculate the standard boiling temperatura.

b. Calculate ∆𝐻 vaporization at 298K and at the standard boiling temperature.
𝑃 2.7738𝑥103
(a) ln ( ) = 20.767 − 𝑇 = ln 105 𝑎𝑡 𝑇 b
𝑃𝑎 −53.08
𝐾
2.7738𝑥103
Tb = + 53.08 = 351𝑘
20.767−ln(105 )
𝑑 ln 𝑝 8.314𝑗𝑚𝑜𝑙 −1 𝑘 −1 𝑥(298)2 𝑥3.6745𝑥103
(b) ∆𝐻 vaporization(298k)=R𝑇 2 =
𝑑𝑇 (298−46.702)2
=43.0kj mo𝑙 −1 at 298k
𝑑 ln 𝑝 8.314𝑗𝑚𝑜𝑙 −1 𝑘 −1 𝑥(352.8𝑘)2 𝑥3.6745𝑥103
∆𝐻 vaporization(351k)=R𝑇 2 =
𝑑𝑇 (352.8−46.702)2
=40.6kjmo𝑙 −1 at 351k
P8.3 In section 8.8, it stated that the maximun height of a water columna in which cavitation does
Not occur is-9.7m. show that this is the case at 298k.
Combining equations(8.28)and(8.31),

H=𝑝inner-pouter/pg
Bubbles Will from when pouter has the value of the vapor pressure of water.
For the equilibrium
H2O(l)=H2O(g)

∆𝐺 °f (H2O,g)-∆𝐺°f(H2O,l)=-228.6KJmol-1 =8.5KJ mol-1

 ∆𝐺°
For this equilibrium ln 𝐾 p = 𝑅𝑇 =PH2O.g

𝑃
1𝑏𝑎𝑟
−8.5𝑥103 𝐽𝑚𝑜𝑙 −1
= exp [ ]
8.314𝐽𝑚𝑜𝑙 −1 𝐾 −1 𝑥298.15𝐾

P=0.032bar = 3242 Pa

P8.4 Use tsuppose tha Pinne =1atm =101325 Pa

Using P=998Kg m-3

(101325−3242)𝑝𝑎
h = 998𝐾𝑔 𝑚−3 𝑥9.81 𝑚𝑠−2

0he vapor P8.4 use the vapor pressures for tetragllloromethone given in the following table to estimate the temperature and
pressure of the triple point and also the enthalpies of füsiont vaporization, and sublimation.

Phase T(k) P(pa)

Solid 230. 225.7
Solid 250. 905
Liquid 280. 6440
liquid 340. 62.201

To estimate H sublimation, use the vapor pressures of the solid phase,

𝑝2 ∆𝐻𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 1 1
ln =− ( − )
𝑝1 𝑅 𝑇2 𝑇1

𝑝2 225.7𝑝𝑎
ln 𝑅 8.314 𝐽 𝑚𝑜𝑙 −1 𝐾−1 𝑥 ln( )
𝑝1 907 𝑝𝑎
∆𝐻sublimation = 1 1 = 1 1
( − ) −
𝑇2 𝑇1 230.𝐾 250.𝐾
 =33.2KJ mo𝑙 −1

To estimate H sublimation, use the vapor pressures of the liquid phase,

𝑝2 62.501𝑃𝑎
𝑅 ln 8.314𝐽 𝑚𝑜𝑙 −1 𝐾−1 𝑋 ln
𝑝1 6440𝑝𝑎
∆𝐻vaporization = 1 1 = 1 1
− −
𝑇1 𝑇2 280.𝐾 340.𝐾

∆𝐻vaporization =30.0KJ mo𝑙 −1

∆𝐻fusion = ∆𝐻sublimation --∆𝐻vaporization

−1
= 33.2KJ mo𝑙 − 30.0𝐾𝐽 𝑚𝑜𝑙 −1
−1
=3.2 KJ mo𝑙

At the triple point, the solid and liquid have the same vapor pressure.

𝑃𝑠𝑜𝑙𝑖𝑑 ∆H sublimation 1 1
ln ( )= ( − )
𝑃𝑠𝑜𝑙𝑖𝑑, 𝑟𝑒𝑓 𝑅 𝑇𝑠𝑜𝑙𝑖𝑑, 𝑟𝑒𝑓 𝑇

𝑃 𝑙𝑖𝑞𝑢𝑖𝑑 ∆𝐻 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 1 1
ln ( )= ( − )
𝑃 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓 𝑅 𝑇 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓 𝑇

∆𝐻 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 1 1
( − ) + ln 𝑃 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓
𝑅 𝑇 𝑠𝑜𝑙𝑖𝑑, 𝑟𝑒𝑓 𝑇

∆𝐻 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 1 1
= ( − ) + ln 𝑃 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓
𝑅 𝑇 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓 𝑇

1 1 ∆𝐻 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 ∆𝐻 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
= ( − + 𝑅 ln 𝑃 𝑠𝑜𝑙𝑖𝑑 − 𝑅 ln 𝑃 𝑖𝑞𝑢𝑖𝑑 , 𝑟𝑒𝑓)
𝑇 ∆𝐻 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 − ∆𝐻 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 𝑇 𝑠𝑜𝑙𝑖𝑑, 𝑟𝑒𝑓 𝑇 𝑙𝑖𝑞𝑢𝑖𝑑, 𝑟𝑒𝑓
For

Psolid, ref =225.7 Pa ,p liquid, ref =6440 pa

T solid , ref = 230.K, Tliquid, ref =280.k

1 1 33.2𝑥103 𝐽𝑚𝑜𝑙−1 30.0𝑥103 𝐽 𝑚𝑜𝑙−1 225.7 𝑝𝑎
= 3 −1
𝑥⌊ − + 8.314𝐽 𝑚𝑜𝑙−1 𝐾 −1 𝑥 ln ( )⌋
𝑇 𝑡𝑝 (33.2 − 30.0)𝑥 10 𝐽 𝑚𝑜𝑙 230. 𝐾 280. 𝐾 6440𝑝𝑎

=2.92x10-3K-1 Ttp=342K

The pressure at the triple point can be obtained from either the equatin for vapor pressure of the solid
or the solid phase.
∆𝐻 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 1 1
𝑃 𝑠𝑜𝑙𝑖𝑑 = (𝑇) = 𝑃 𝑠𝑜𝑙𝑖𝑑 , 𝑟𝑒𝑓 𝐸𝑋𝑃 ⌊ ( − )⌋
𝑅 𝑇 𝑠𝑜𝑙𝑖𝑑 , 𝑟𝑒𝑓 𝑇
33.2𝑥103 𝐽𝑚𝑜𝑙 −1 1 1
𝑃 𝑡𝑝 = 225.7 𝑃𝑎 𝑥 𝑒𝑥𝑝 ⌊ 𝑥( − )⌋
8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 230. 𝐾 342𝐾
Ptp =6.70x104 Pa

P8.S Within what range can you restrict the values of P and T if the following information is
known about C02 ? Use Figure 8.12 to answer this question,

a. As the temperature is increased, the solid is first converted to the liquid and
subsequently to the gaseous state.

b. An interface delineati.ng liquid and gaseous phases is observed throughout

the pressure range between 6 and
65 atm.

c. Solid, liquid, and gas phases coexist at equilibrium,

d. Only a liquid phase is observed in the pressure range from 10. to 50. attn.

e.' An increase in temperature from —80.0 to 20.0C converts a solid to a gas with no intcrmcdiate liqu

(a) The temperature and pressure are greater than the values for the triple
point, —56.60C and 5.11 attn.

(b) The temperature lies between the values for the triple point and the critical
point.

(c) The system is at the iriple point; —56.69C and 5.11 attn.

(d) The temperature lies between the values for the triple point and the
critical point.
 (e) The pressure is below the triple point pressure value of 5.1.1 atme

P8.6 -A phase diagram for potassium is shown below.

a. Which phase has the higher density, the fcc or the bcc phase? Explain your ansvver.
According to Le Chatelier's principle, for a given lemperature, the phase with
the higher density will be found at higher pressure. Therefore the luc phase is
more dense.
b. Indicate the range of P and T in the phase diagratn for which fcc and liquid potassium are in
equilibriurn. Does fcc potassium float on or sink in liquid potassium? Explain your answer.

fee and liquid potassium are in equilibrium on the liquid—solid coexistence

line existing upward from the triple point. The fcc phase will sink in the liquid
because the slope of the two phase liquid—solid coexistence line is positive.
c. Redraw this diagram for a different pressure range and indicate where you expect to find
the Vapor phase. Explain how you chose the slope or your Jiguid-vapor coexistence line.

The phase diagram would look like Figure 8.4 except that there is a second
triple point at which the liquid and the lt•c and bcc solid phases coexist. The
vapor phase is found a! much lower pressures and higher temperatures. The
slope of the vapor—liquid coexistence line is always positive because the
vapor pressure increases rather than decreases with increasing temperature.

P8.7 A cell is roughly spherical with a radius of 20.0 x 10 m. Calculate the work required to
expand the cell surface if the radius increases by a factor of three. Assume the cell is
surrounded by pure water and that T 298, 15 K,

Area1=4ꙥr2 =4ꙥ(20.0x10-6 m)2 =5.03x10-9 m2

R2 =3rl =60.0 x 10-6 m

Area2 =4ꙥr22 = 4ꙥ(60.0 x 10 -6 m) =4.52 x 10-8 m2

The surface tension of water is listed in Table 8.5.

P8.8 It has been suggested that the surface melting of ice plays role in enabling speed skaterg
to achieve peak performance. Carry out the t following calculation to test this
hypothesis. At l atm pressure, ice melts at 273.15K,∆𝐻 𝑓𝑢𝑠𝑖𝑖𝑜𝑛 =
6010. 𝐽𝑚𝑜𝑙 −1 ,the density of ice 920.kg m-3. And the density of liquid water is
997kg-3..

a. What pressure is required to lower the melting tcmpcraturc by 4.00C?

b. Assume that the width of the skate in contnct with thc ice has been rcduced by
sharpening to 19 x 10"3 cm, and that the lcngth of the contact nrcn is 18 Ctn. If a
skater of mass 78 kg is balanced on one skate, what pressure is cxertcd nt the
intcrfnce of the gkntc nnd tho ice?
c. What is the melting point of ice under this pressure?
d. If the temperature of the ice ig --4.00C, do you expect melting oftlle ice at the ice-
skate interface to Occur?

𝑑𝑝 ∆𝑆 𝑓𝑢𝑠𝑖𝑜𝑛 ∆𝑆 𝑓𝑢𝑠𝑖𝑜𝑛 22.0𝐽 𝑚𝑜𝑙 −1 𝐾−1

(a) ( )fusión = = 𝑀 𝑀 = 18.02𝑋10−3 𝐾𝑔 18.02𝑥10−3 𝑘𝑔
𝑑𝑡 ∆𝑉 𝑓𝑢𝑠𝑖𝑜𝑛 − −
𝑃𝐻2𝑂,1 𝑃𝐻2𝑂.𝑆 997𝑘𝑔 𝑚−3 920𝑘𝑔 𝑚−3

=-1.45x107 pa K-1 =-145bar K-1

The pressure must be increased by 582 bar to lower thc melting point by 4.00C.

𝐹 78𝐾𝑔 𝑥 9.81𝑚𝑠 −2
(b) P =𝐴 = 18𝑥10−2 𝑚𝑥19𝑥10−5 𝑚 = 2.24𝑥107 𝑝𝑎 = 2.24𝑥102 𝑏𝑎𝑟
𝑑𝑇 1°𝐶
(c) ∆𝑇 = (𝑑𝑃)fusión ∆𝑃 = 145 𝑏𝑎𝑟 𝑥2.24𝑥102 𝑏𝑎𝑟 = 1.5°𝐶 Tm =-1.5°c

(d) No, because the lowering of the melting temperature is less than the

temperature of the ice.

P8.9 Answer the following questions using the phase diagram for carbon sketched below

a. Which substance is denser, graphite or diamond? Explain your answer.

According to Le Chatelier's principle, for a given temperature, tho phase with
the higher density will be found at higher pressure. Thcreforc diamond is
more dense than graphite.

b. Which phase is more dense, graphite or liquid carbon? Explain your answer.
Graphite is more dense because the slope of the graphite-liquid coexistence
line is positive.