5.27: Graphite is more compressible than diamond.

(a) Taking compressibility into account, would you expect the transition from graphite to diamond to occur at higher or lower pressure than predicted in the text? Thepressurepredictedinthetext(pg. 170) is15kbar. V G V =?P T T T So, as the pressure rises, V decreases and G,forgraphite,increases more slowly. Thus,it be expected that the transition will occur at slightly higher pressure. (b)The could isothermal compressibility of graphite is 3 106 bar1, while that of diamond is more than ten times less and hence negligible in comparison -isothermal ? compressibility is the fractional reduction in volume per unit increase in ? pressure, as dened in Prob. 1.46. Use this information to make a revised estimate of the pressure at which diamond becomes more stablethangraphite(at roomtemperature) T, is: From 1.46, the isothermal compressibility, Since: T 1 V =3 106 bar1 =2.956 1011 Pa1
? ?

?G

Therefore, PVd + God = PVg TVg/2P2 + Gog where God = God +2900J ?G and: 2 TVg PVd +2900 = PVg P 2 TV g 2 P +(Vd Vg)P 2900 =0 ?P 2 Solve in the usual way:
T

= V (Vg Vd) (Vg Vd)2 4 ?P P= 1.89 10 m3

6 = T

m 1.63 10

Vg T ? 2900 P = 2 T Vg 2 2 3 6 V0(1??TP)

? ?G = ? P P0 V0(1??TP)dP = PV0 ? ?TP2 2

(b) Calculate the pressure (still at room temperature) at which the other phase should become stable? However, the situation changes whenpressureisincreased. Recall that theGibbsfree energy is of theform G = U+PV TS . Therefore, as thepressure increases, theGibbsfree energy of the material with the large volume increases more rapidly, and, at high enough pressure, the material with the smaller 3 36.93 cm3 be more stable. The molar volume aragonite, volume will compared to the molar volume ofof calcite is which is 34.15 cm . Therefore, above some pressure, aragonite will be more stable. At constant temperature, we can write: G dG = dP = vdP or G(T0,P) =G(T0,P0)+V(PP0) P T where T0=298K and P0=1bar, and where wehave assumed thatthe volumedoes not change appreciably with increase in pressure. Therefore, the pressure at which the free energy of calcite(Gc)willbe equal tothefree energy of aragonite(Ga)is given by Gc(T0,P0)+Vc(P P0)= Ga(T0,P0)+Va(P P0) Gc(T0,P0)Ga(TP,P0) 0 = Va Vc 0 P P P0 = (1128.8kJ)(1127.8kJ) (34.15 cm3)(36.93 cm3) 8 1.02 3 J 10 P P0 = =3.6 10 Nm

1.569 1016 3Pa1 m So, P =1.64 109 Pa or P =2.24 1010 Pa. So, with the lowest value, P =16.22kbar 5.28: Calcium Carbonate, CaCO3, has two common crystalline forms, calcite and aragonite. Thermodynamic data for these phases can be found at the back of the book. (a)Which is stable at the earths surface, calcite or aragonite? calcite aragonite fG (kJ/mol) -1128.8 -1127.8 S (J/(Kmol) 92.9 88.7 V (cm3) 36.93 34.15

G(T2)=G(T1) S(T)dT
T1

T2

Although the entropy of any given phase will increase signicantly as the temperature increases, aboveroomtemperatureitisoftenagood approximationtotakeS, the dierence in entropies between two phases, to be independent of T. This is because the temperature dependence of S is a function of the heat capacity -as we saw in Chapter 3 -and the heat capacity of a solid athigh temperaturedepends,to agood approximation, only onthe number of atoms it contains. For either phase, G T =
T S

and if we integrate this expression from T1 to T2: dG = S(T)dT

G1 T 1 G2 T 2

G(T1)G(T2)= S(T)dT
T1

T2

Ifwedothe sameprocessforthetwophases andthen subtractthetwo, G(T1)G(T1) G and S(T)S(T) S(T)and so we obtain: G(T2)=G(T2.78 10 1) S(T)dT m3 T1 So, P = 3.6 kbar. Therefore, aragonite is expected to be more stable at which was in excess of result. pressures the desired 3.6 kbar. A more accurate calculation should include any change in S to be with increase of T, nd theusing data on the compressibility of (c)Taking volume independent in pressure, range of temperatures over which the materials. kyanite, andalusite and sillimanite should be stable -at 1 bar. If S is be 5.29: Aluminium silicate, Al2SiO5, has three dierent crystalline forms: kyanite, andalusite, and sillimanite. Because eachtaken outside the integral: independent of T,S(T) S and it can be is stable under a dierent set of temperature-pressure conditions, and all are commonly found in metamorphic T2 G(T2) = indicators dT rocks, these minerals are important G(T1)S of the geologic history of rock T1 bodies. (a)Referring to the thermodynamic data at the back of the book, argue that at G(T2) = G(T1)(T2 T1)S 298 K the stable phase should be kyanite, regardless of pressure. kyanite andalusite sillimanite fH (kJ/mol) If-2594.29 -2590.27the temperature at which the phase change occurs -the two we take T2 to be -2587.76 fG (kJ/mol) -2443.88 in equilibrium -then phases are-2442.66 -2440.99 G(T2)=0. Solving for T2 then gives simply: S (J/(Kmol) 83.81 93.22 96.11 V (cm3) G(T1) 44.09 51.53 49.90 T2 = T1 + S At temperature 298 K and pressure 1 bar, kyanite, which has the lower free energy, is G stable. Thermodynamicdatais onlyavailable at298K, so this valueis T Forthekyanitemore Furthermore, it also has the lowest molar volume, V, and 1since V = , this T, andalusite transition, G(T1)=1.22kJ(foronemoleof material),whileS = phases. means that its G value rises more slowly than those of the other two 9.41 J/K. P N Therefore, the out at a lowerat which the andalusite becomes more stable than Since it starts temperature value and increases slowest, it will never intersect kyanite should be approximately: This is in contrast to the graphite-diamond the G values of the other phases. case as consider what happens at xed pressure as we vary the temperature. (b)Now illustrated in gure 5.5. 1.22kJ T2 =298K+ =428K Let G be the dierence in Gibbs free energy between any two phases, and 9.41J/K similarly for S. Show
T2 6

2.89kJ T2 =298K+ =533K 12.30J/K and, nally, for the andalusite-sillimanite transition: 1.67kJ T2 =298K+ =876K 2.89J/K So, at atmosphericpressure, kyanite shouldbe stable up to approximately428K, andalusite should be stable from 428 K to 876 K and sillimanite should be stable above 876 K. to to the room-temperature heat capacities of the three forms of (d) Referring Al2SiO5, discuss the accuracy of the approximation S=constant. The change in entropy as the temperature is increased is given by eqn. 3.50: T2 C S(T2)= S(T1)+P dT T1 T Asinthepreviousquestion,if we writethisexpressionforthetwophases and then subtract them, we obtain: S(T2)=S(T1) CPdT
T1 T2

To take a rough estimate by assuming that CP is independent of temperature, we obtain: T1 S(T2) = S(T1)+CP ln T2 Taking the kyanite-andalusite transition, CP=1.01J/K(at roomtemperature). Taking T1 = 298 K and T2 = 248 K, the last term in the above expression is 0.37 J/K which is much smaller than S(T1)=9.41 J/K, and it can be concluded that over this range S is reasonably independent of temperature. However, if we take the andalusite-sillimanite transition, here CP=1.80 J/K and we take T2=876 K. Using these numbers, the last term is now1.94J/Kwhich certainly compares withS(T1)=2.89J/K.Here,S variesby nearly 70% over the temperature range of interest. Here it is the concluded that the calculated temperature of thetransition couldbe oby asmuch as100-200K.To make a signicantly improved calcuation, it would be necessary to have the heat capacity data as a function of temeprature. 5.32: The density of ice is 917 kg/m3 . (a) Use the Clausius-Clapeyron relation to explain why the slope of the phase boundary between water and ice is negative. As ice melts into water the change in entropy -or latent heat -is positive, while the change in volume is negative, since ice is less dense. As such, the slope of the phase boundary, given by S/V, must be negative. From a more fundamental perspective, converting ice to water lets the entropy of the environment increase -by making more volume available and thiseectismoreimportant athigherpressure since P = T(S/V). So highpressures tend to push the equilibrium in the direction of the phase that takes up less volume.

Its easiertothink ofjust onegram ofice and not one mole. Thelatentheatisthen333J, and the volume of theiceis(917,000)1 m3 =1.091106 m3 , and the volume of the water is 1.000 106 m3 . The slope of the phase boundary is then: dP L 333J == dT TV (273K)(0.091 106 m3) dP 7 = 1.35 10 Pa/K= 135bar/K dT So, if the temperature decreases by one degree -from 0 C to -1 C, the pressure must increase by 135 bars to remain on the phase boundary. In other words, ice will melt at -1 Cif thepressureis above135bars(or133 atmospheres). (c)Approximately how deep under a glacier would you have to be before the weight of the ice above gives the pressure found in the previous question? Note that the pressure can be greater at some locations, e.g. where the glacier ows over a protruding rock. uid,thentheincreaseinpressureat adepth z isjust gz If wetreattheglacierasa where is the density. This is obtained by considering a column of ice, depth z, with unit area A=1m2 . The weight of the column is then mg = Agz = gz, and this must be balanced by the pressure from below. In this case, to reach a pressure of 135 bars: P 135 105 N/m2 z = = =1500 m g (917kg/m3)(9.8N/kg) This is an interesting result, since its a huge depth. It also means that the ow of glaciers is apparently not caused primarily by the lowering of the melting point underrough estimate of the pressure under the blade of an ice skate, and (d) Make a pressure. calculate the melting temperature of theiceatthispressure. Someauthorshave claimed that skaters glide with very litte friction because of the increased pressure under the blade melts the ice to create a thin layer of water -what do you think of this ice skate is a few mm while its length is about 25 cm. The total The blade of an explanantion? area is then only about 10 cm2 . Even when turning, and leaning on the corner of the blade, the total area in contact with the ice is probably more than 1 cm2 = 104 m2 . With an approximate mass of 50 kg, giving a weight of about 500 N, the pressure on the blade is (500N)/(104 m2)=5106 Pa =50bars. Underthispressure,themelting temperature of ice drops by only 50/135 0.4 C. This mechanism of friction reduction would work only if the ice temperature is already within less than half a degree of melting and, even then, only whenyoure minimizing theareaof thebladeincontact with theice. Inpractice, the ability to glide doesnt depend so critically on the ice temperature or on how the blade touches the ice, so on boiling 5.36: Eect of altitude this mechanism is not likely to be important. water. (a)Use the result given in problem 5.35 and the data in Figure 5.11 to plot a graph of the vapour pressure of water between 50 and 100 . how well can you match the data at the two end points? Eqn from problem 5.11:
RT P = ce

one of the given endpoints, i.e. 50? P c = e? L RT 1.234* 10?1 c = e = 7.077* 10?5 bar
?
41.79*103 (8.31)(323)

(a) Use the vapourpressure equation(Problem5.35) anddatafromFigure5.11 toplot a graph of the vapour pressure of water from 0 C to 40 C. Notice that the vapour
pressure approximately doubles for every 10 C increase in the temperature.

The vapour pressure equation is: P = De

L RT

We can rst get constant looking at the data for T=25 C: Use this value with the average value of L to calculate the 43990J/mol L RT pressure: D = Pe =(0,0317bar)exp =1.6296 106 bar (8.31J/(Kmol))(298.15K) ffd8ffe000104a4649460001020101200120000 0ffe20c584943435f50524f46494c45000101000 of T, so use aquadratic,i.e. L = Next,its necessary toget values of L as afunction 00c484c696e6f021000006d6e74725247422058 40 C: Which gives: a =5.456 a+bT+ cT2 to t to the data between 0.01 C and 595a2007ce0002000900060031000061637370 104 J/mol,b= ffd8ffe000104a4649460001020101200120000 4d534654000000004945432073524742000000 0ffe20c584943435f50524f46494c45000101000 0000000000000000000000f6d6000100000000 00c484c696e6f021000006d6e74725247422058 d32d4850202000000000000000000000000000 595a2007ce00020009000600310000616373704 00000000000000000000000000000000000000 d5346540000000049454320735247420000000 00000000000000000000000000000011637072 000000000000000000000f6d6000100000000d3 74000001500000003364657363000001840000 2d485020200000000000000000000000000000 006c77747074000001f000000014626b707400 00000000000000000000000000000000000000 000204000000147258595a0000021800000014 00000000000000000000000000001163707274 6758595a0000022c000000146258595a000002 00000150000000336465736300000184000000 4000000014646d6e640000025400000070646d 6c77747074000001f000000014626b707400000 6464000002c400000088767565640000034c00 204000000147258595a0000021800000014675 00008676696577000003d4000000246c756d69 8595a0000022c000000146258595a0000024000 000003f8000000146d6561730000040c000000 (b)Readingthegraphbackwards, estimatetheboiling temperature of water 000014646d6e640000025400000070646d6464 2474656368000004300000000c725452430000 atthelocation you calculated in Problem 1.16 -i.e. Mt. Everest. Exaplain why it 000002c400000088767565640000034c0000008 in 2the mountains. values of L 043c0000080c675452430000043c0000080c62 takes longer1to cook noodles = 2.430 102 J/(molK ). Using these, ffd8ffe000104a4649460001020101200120000 2.819 10 J/(molK), and c when youre camping 676696577000003d4000000246c756d6900000 5452430000043c0000080c7465787400000000the vapour pressure calculated 0ffe20c584943435f50524f46494c45000101000 as a 1.16: From function of T can be calculated and 3f8000000146d6561730000040c000000247465 436f7079726967687420286329203139393820 00c484c696e6f021000006d6e74725247422058 according to the above formula. mp 6368000004300000000c725452430000043c000 4865776c6574742d5061636b61726420436f6d z 595a2007ce0002000900060031000061637370 P(z)= P(0)eRT 0080c675452430000043c0000080c6254524300 70616e79000064657363000000000000001273 4d534654000000004945432073524742000000 z(9.822105 00043c0000080c7465787400000000436f70797 P(z)= P(0)e 5247422049454336313936362d322e31000000 0000000000000000000000f6d6000100000000 269676874202863292031393938204865776c6 00000000000000001273524742204945433631 d32d4850202000000000000000000000000000 574742d5061636b61726420436f6d70616e7900 3936362d322e31000000000000000000000000 00000000000000000000000000000000000000 00646573630000000000000012735247422049 000000000000000000000000000000 = 8850 m we get P =0.412 atm Reading 00000000000000000000000000000011637072 Using P(0) = 1 atm and for Everest, z 454336313936362d322e310000000000000000 74000001500000003364657363000001840000 351 K, i.e. 78 . As the height o the temperature at this pressure gives: T 00000012735247422049454336313936362d32 006c77747074000001f000000014626b707400 temperature at which H2O boils increases, the atmospheric pressure and the 2e310000000000000000000000000000000000 000204000000147258595a0000021800000014 decreases. However, the 00000000000000000000 noodles still need energy to cook and since the water 6758595a0000022c000000146258595a000002 get this energy. boils at a lower temperature, the noodles dont 4000000014646d6e640000025400000070646d 6464000002c400000088767565640000034c00 5.42:Ordinarily,thepartialpressure of water vapourinthe airislessthanthe 00008676696577000003d4000000246c756d69 equilibrium vapour pressure at the ambient temperature; this is why a cup of 000003f8000000146d6561730000040c000000 water will spontaneously evaporate. The ratio of the partial pressure of water 2474656368000004300000000c725452430000 vapour to the equilibrium vapour pressure is called the relative humidity. When 043c0000080c675452430000043c0000080c62 the relative humidity reaches 100%, so that water vapour in the atmosphere (b)The in duusive on a certain summer day 5452430000043c0000080c7465787400000000is 30 C(not so often the air is would be temperatureequilibrium with a cup of liquid water, we say thatin Sweden, 436f7079726967687420286329203139393820 is not a sponge that can hold obviously). What this term is incorrect since air saturated (although is the dew point if the relative humidity is 90%? What if the 4865776c6574742d5061636b61726420436f6d is mostly empty only a certain amount40%? relative humidity is of water -even saturated air 70616e79000064657363000000000000001273 P 5247422049454336313936362d322e31000000 = 00000000000000001273524742204945433631 De ?L RT 3936362d322e31000000000000000000000000 ? 000000000000000000000000000000

=e D P

L RT

L L P = De RT =0.046113bar

To ndthedewpointif weareat90%humidity(P =(0.9)(0.046113) = 0.041502 bar. ln We have to solve the vapour pressure equation for T: = ?

D RT

P D ?L = RT ln D ? L = RT ln P (? nature of ln function) L

Fromthegraph,PV (35C)=0.06661bar sothepartialpressureis,PPH2O =(0.9) (0.06661bar) = 0.05995bar. Using this value: PPH2 O 0.06661bar relhum = = =630% PV(10C) 0.00944bar So, we are well over the dew point! 6.3:Considerahypothetical atomthathasjusttwostates: aground statewith zeroenergy and an excited state with energy2 eV.Draw agraph of thepartitionfunctionfor this system asafunctionof temperature, and evaluatethepartitionfunctionnumerically at T =300 K, 3000 K, 30,000 K and 300,000 K. The partition function, Z, is given by: Rln where E(s)is the energy of state s. Inthisquestion, wehavetwo states(s=2) and E(0)= 0eV(= 0J) and E(1)=2eV(= 3.204 1019 J). The graph of Z vs T is given However, we know that L L(T)and we used earlier L(T)= a + bT + here: ffd8ffe000104a4649460001020101200120000 T= == cT2, so: L(T) a + bT + cT2 a + bT + cT2 0ffe20c584943435f50524f46494c45000101000 D D e Rln Rln P P 00c484c696e6f021000006d6e74725247422058 D 595a2007ce0002000900060031000061637370 where e = Rln for convenience. So, P 4d534654000000004945432073524742000000 0000000000000000000000f6d6000100000000 2 a + bT + cT T= d32d4850202000000000000000000000000000 e eT = a + bT + cT2 00000000000000000000000000000000000000 0= cT2 +(be)T + a 00000000000000000000000000000011637072 74000001500000003364657363000001840000 006c77747074000001f000000014626b707400 which we can solve quadratically: 000204000000147258595a0000021800000014 6758595a0000022c000000146258595a000002 (e b) (be)2 4ca T 4000000014646d6e640000025400000070646d = 6464000002c400000088767565640000034c00 2c T (K) and the value of Z at the xed points is: 00008676696577000003d4000000246c756d69 Z 000003f8000000146d6561730000040c000000 300 D 2 Usinge = Rln = 1.45410 J/(Kmol),a =5.456104 J/mol,b= 2.819101 J/ 2474656368000004300000000c725452430000 P 1 (molK), and c = 2.430 102 J/ 043c0000080c675452430000043c0000080c62 3000 2 5452430000043c0000080c7465787400000000 (molK ): T =301.66K(= 28.66 1.00043545 436f7079726967687420286329203139393820 C). If the relative humidity changes to 40%, P =(0.4)(0.046113) = 0.018445 bar. Here, T 30000 4865776c6574742d5061636b61726420436f6d = 1.46120482 291.1K(= 18.13 C) 70616e79000064657363000000000000001273 300000 5247422049454336313936362d322e31000000 1.92552762 a relative humidity of 90%. 5.43: Assume that the air you exhale is at 35 C, with 00000000000000001273524742204945433631 This air immediately mixes with the environmental air at 10 C and unknown 3936362d322e31000000000000000000000000 relative humidty: during the mixing, a variety of intermediate temperatures and 000000000000000000000000000000 water vapour percentages temporarily occur. If you are able to see your breath due to the formation of cloud droplets during this mixing, what can you conclude about the relative humidty of your environment? Refer to the vapour pressure graph we have air at 355.42. So, drawn in problem C, with a relative humidity of 0.9 into air at 10 C, with a relative humidity of ?. Since we can see our breath: relhum = PPH2 O PV(35C) T=
D P

Z=e

E(s)

kT

e P(s)= Z So, P(1) = 6.923/8.067 = 0.858, P(2) = 1.000/8.067 = 0.124, and P(3) = 0.144/8.067 = 0.018. (c)Becausethe zeropointformeasuring energiesisarbitrary, we couldjust aswell say that the energies of the three states are 0 eV, 0.05 eV and 0.10 eV, respectively. Repeat parts (a)and(b) using these numbers. Explain what changes and whatdoesnt. The energy of the three states is now: E(0)=0eV,E(1) =0.05 eV, andE(2) =0.10 eV:
ffd8ffe000104a4649460001020100c800c80000ffe20c584 ee Z =1.000+0.144+0.021 943435f50524f46494c4500010100000c484c696e6f021000 006d6e74725247422058595a2007ce00020009000600310 =1.165 000616373704d5346540000000049454320735247420000 000000000000000000000000f6d6000100000000d32d485 02020000000000000000000000000000000000000000000 So, the partition function is smaller. However, as expected, P(1) = 1.000/1.165 00000000000000000000000000000000000000000000000 = 0.858, P(2) = 0.144/1.165 = 0.124, and P(3) = 0.021/1.165 = 0.018. i.e. the 00000116370727400000150000000336465736300000184 0000006c77747074000001f000000014626b70740000020 probabilities are exactly the same. 4000000147258595a00000218000000146758595a000002 2c000000146258595a0000024000000014646d6e6400000 6.6:Estimatetheprobability that ahydrogenatomat roomtemperatureisinoneofits 25400000070646d6464000002c400000088767565640000 rst excited states 034c0000008676696577000003d4000000246c756d69000 -relativetotheprobability ofbeing intheground state. 003f8000000146d6561730000040c000000247465636800 0004300000000c725452430000043c0000080c675452430 Dontforgettotake degeneracy into account. Repeat the calculation for a hydrogen 000043c0000080c625452430000043c0000080c74657874 atom in the atmosphere of UMa, whose surface temperature is approximately 00000000436f70797269676874202863292031393938204 865776c6574742d5061636b61726420436f6d70616e79000 9500 K. The ratio is given by: 06465736300000000000000127352474220494543363139 36362d322e3100000000000000000000001273524742204 9454336313936362d322e31000000000000000000000000 n P(S2)(E2E1) kT =e 0000000000000000000000000000002.58102 + 2.58102 P(S1) n1
00.05 0.10

E(s) kT

+ e 2.58102 where E,n and the energy and degeneracy of the state. From gure 6.2, for hydrogen, n1 = 1 and E1 = -13.6 eV, while n2 = 4 and E2 = -3.4 eV. kT =(6.203 0.82 J/K)(5800 K) = 1023eV: P(S2)4 = e
(3.413.6) 0.5

P(S1)1 P(S2) =5.44 P(S1) 9 10 6.5: Imagine a particle that can be 23only three states, with energies -0.05 eV, 0 Now, for UMa, kT =(6.203 10 in J/K)(9500K) =0.5 0.05 eV. This particle is in equilibrium with a reservoir at eV: eV, and P(S2)4 300 K. (a)Calculate the partition function for(3.413.6) this particle. 0.82 =e P(S1by: )1 The partition function, Z, is given E(s) P(S2) =1.55 105 Z = e kT s P(S1)

where E(s)is the energy of state s. For a change, kT =4.14 1021 J =2.58 102 6.7:and the energy of theatom states shown in 0.05 eV,E(1) =0eV, two-fold eV Each of the hydrogen three states: E(0)= Figure 6.2 is actually andE(2) degenerate, because the electron can be in two independent spin states, both 0.05 0 0.05 =0.05 eV: 2.581022.581022.58102 Z= +e+ with essentially the same eenergy.e Repeatthecalculationfortherelativeprobability ofbeing inthe rstexcited state, taking spin degeneracy into account. Show that Z =6.923+1.000+0.144 =8.067 the results are unaected.

P(S1) n1

P(S2) n (E2E1) 2 = e kT

Since we now include the extra degeneracy of the spin, n1 2n1 = 2 and n2 2n2 = 8. This still gives the same n2/n1 ratio as before. 6.12:Coldinterstellarmolecularcloudsoftencontainthemoleculecyanogen,CN,whose rst rotational excited states have an energy of 4.74 eV above the ground state. There are actuallythree such excited states, all with the same energy. In1941studies of the absorption spectrum of starlight that passes through these molecular clouds showed that for every ten CN moleculesthatareintheground state,approximately threeothersareinthe rstthree excited states -that is, an average of one in each of these three states. To account for this data, astronomers suggested that the molecules might be in thermal equilibrium with From the observations: some reservoir with a well-dened temperature. What is that temperature? P(S2)3 = P(S1) 10 and from the knowledge of the degeneracies: P(S2)3 (E2E1) 3 kT =e= P(S1)1 10 Rearranging: 3 (E2 E1) 3 kT e= 1 10 (E2 E1) 1

kT = e (E2 E1) kT

10

E2 E1 k ln10 Here, E2 E1 isjustthe energy dierencebetweenthe energy levels,i.e. 4.74 eV. From this, T = 2.37 K, i.e. the cosmic microwave background. T= 6.13:At veryhigh temperatures, asintheearly universe,theprotonand theneutroncanbe thought of as two dierent states of the same particle, called the nucleon. The reactions that convert a proton to a neutron or vice versa require the absorption of an electron or a positron or a neutrino, but all of these particles tend to be abundant at high temperatures. Since the neutrons mass is slightly heavier than the protons by 2.31030 kg, its energy is higher by this amount times c2 . Suppose, then, that at some very early time, the nucleons were in thermal equilibrium with the rest of the universe at 1011 K. What fraction of the nucleons at that time were protons and what fraction were neutrons? neutron lies Since they are dierent states of the same particle, but that the slightly higher in energy, we consider theproton as thegroundstate, with E(1), andthe neutron with E(2).

E2 E1 k T

e = 10 =ln10

E2 E1 =mc 1016 2 2)2.07 1013 J 30 E2 E1 = (2.3 10 kg)(9.0ms = E2 E1 =1.29 106 eV If we assumethattheground state energyis0 eV(E(1) =0;eV) thentheenergy ofthe higher state is: E(2) =1.29 106;eV Using kT = (6.023 1023 J/K)(1.0 1011 K) = 1.38 1012 J =8.61 106 eV, we can now calculate the partition function:

E(s)

Z=e
s 0

kT 1.29106 8.61106

Z=e+e Z = 1+0.8607 =1.8607 Now,theprobabilities arejust: P(S)= So, 10.8607 P(1) = ,P(2)= 1.86071.8607 P(1) 0.5374,P(2)=0.4636 = expkT Z
E(s)

The fraction that are protons is 0.5374 and the fraction that are neutrons is 0.436. 6.16: Prove that, for a systemin equilibrium with a reservoir at temperature, T, the average value of the energy is: 1 Z E = = lnZ Z From equation 6.16 we know that: 1 E(s)E(s) E = E(s)e, whereZ = e Z So, Z E(s) =e s Z E(s) =e s Z E(s) = E(s)e s Z E(s) = E(s)e s
ss

E(s)

E = E(s)e = Zs Similarly,

E(s)

ln(Z) = ln e s So, lnZ = 1 1 lnZ = Z s e 11 Z s Z s Thus, E = lnZ 6.23: For a Co molecule, the constant is approximately 0.00024 eV, where this number is measured using microwave spectroscopy, that is by measuring the microwave frequencies needed to excite the molecules into higher rotational states. Calculate the rotational partition function for a CO molecule at room temperature, 300 K, rst using the exact formula (6.30)and then using the approximateformula(6.31). Using the approximate formula, 6.31: kT 2.58 102 eV Zrot = =107.68 2.4 104 eV From formula 6.30: Zrot = (2j+1)e = (2j+1)e
j=0 j=0 30 2

lnZ = lnse

E(s)

e ss E(s) e

E(s)

E(s)

lnZ = E(s)e = E(s)e

E(s)

E(s)

E(j)

j(j+1)

kT

kT

= 1+3e +5e 6 +7e 12 +9e 20 +11e 110 42 56 72 90 13e +15e +17e +19e +21e 240 132 156 182 210 23e +25e +27e +29e +31e
420 272

33e

600

+35e

306

+37e

342

+39e

380

+41e

 6.29: Although an ordinary H2 molecule consists of two identical atoms, this is not the case for the molecule HD, with one atom of deuterium, i.e. heavy hydrogen 2H Because of its small moment of inertial, the HD molecule has a relatively large value of :0.0057 eV. At approximately what temperature would you expect the rotational heat capacity of a gas of HD moleculesto freezeout,thatit,tofall signicantlybelowtheconstant valuepredicted by the equipartition theorem? that: With the assumption kT 1 we get: 4 T =0.00578.65 10 eV/K k T 6.6K 6.35: Verify from the Maxwell speed distribution that the most likely speed of a molecule is 2kT/m The most likely speed will be given by the where the derivative of the distribution is equal to zero: d dm
mv

dv dv 2kT

D(v)= 4v2 e =02kT

3/2 md 2mv 2kT =4 ve 2 2kT dv m 2mv mv3/ mv 2kT 2kT 22 =4 2ve e 2kT kT 3/ 2 m mv mv 2 =4ve 2 2kT 2kT kT

3/2 2

Now, if the derivative is set equal to zero, this only requires that the terms in the bracket equal zero: d dv D(v) = 0
2

mv 2 =0 kT 2 mv =2 kT 2k v2= T m and, nally, + 43e

462

+ = 107.87

2kT v 506 +47e +45e = m

552

+49e

6.48: For a diatomic gas get four digits! It took only 25 terms to near room temperature, the internal partition function is simply the rotational partition function computed in Section 6.2, multiplied by the degeneracy Ze of the electronic ground state.

Using,

? ?

?F S = ? S = Nk ln + VZeZrot 7 NvQ 2

?T V,N Calculatethe entropy of a mole of oxygen(Ze = 3) at room temperature and atmospheric pressure, and compare to the measured value at the back of the book. Starting with: F = kT lnZ where, ZeZrot,Zrot = or ? Therefore,
? ? ?

kT kT 2

F = kT [N lnV + N lnVint N lnvq N lnN +1] F S = NkT lnVint F = = NkT [lnV lnvq lnN +1]+ NkT [lnV ?lnvq ?lnN + 1]+ NkT NkT [lnV lnvq lnN +1]+ Fint ? ? ?T lnvq ? ?Fint ?T
V,N

? ? ? ? ? ?

S = Nk ln V +1 + 3 Nk ? ?Fint

Nvq Richard Thomas -FK4005 Thermodynamik -Solutions to Raknovningar 16 To calculate the entropy of 1 mole of oxygen(Ze =3) we need: kT (8.617 105 eV/K) 2 and Zrot == (298K) ?T 2 2(0.00018 eV) Zrot 71 h
? ?3 ?
V,N

6.63* 10?34 Js
?3

vq = ? =??
?

where we have used the result: 3 lnvq = T 2T To evaluatethelastterminthe expressionforS, we need Fint = NKT lnZint = NkT lnZrotZe Therefore, Fint NkT Zrot = Nkln(ZrotZe)+ Ze + Nk T ZrotZe T which gives: V3 S = Nk ln +1 + Nk + Nk+ NklnZint Nvq 2 S = Nk ln + VZint 7 Nvq 2