6 views

Uploaded by captainhass

- Memorization List (Mine)
- introduction to separation technology
- Chapter 1~ Notes Sept 2015
- Equilibrium Practice Problems Answers
- Long Test 62009 Gas Laws
- Oil & Gas Processing Engineering & Science
- (968)-chemistry-gyan-sutra-jee-main.pdf
- Liquids and Solids Test Answers
- A Study of the Equilibrium between Ferric and Thiocyanate Ions
- Physical properties of Sodium Niobate (NaNbO3) at different phase transitions
- Vapor-Liquid Equilibrium of the CH4-CO2 System at Low Temperature
- 10.Phase Diagrams.pdf
- AP '84 Multiple Choice
- Exp5-Autosaved
- Free Energy of Formation of Al(OH)3
- cmc chapter 12
- CHE3165 Test 2 (2011).pdf
- kech107
- 2006 Chem 1112
- 42_2_SAN FRANCISCO_04-97_0485

You are on page 1of 7

http://ocw.mit.edu

Spring 2008

For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.

5.60 Spring 2008 Lecture #29 page 1

treated so far with macroscopic thermodynamics

Separated atoms

0

Products Reactants

E energy levels

−εr = -D0,r

−εp = -D0,p

Chemical equilibria

Gas phase: Calculate Kp from microscopic properties

aA + bB F cC + dD

Q = (qtrans

N

N ! ) qint

N

G = −kT lnQ + NkT = −NkT ln (qtrans qint N ) = −NkT ln (q N )

For molecules in the gas phase, internal degrees of freedom are rotations and

vibrations and electronic states.

5.60 Spring 2008 Lecture #29 page 2

qelec = e D 0 kT

Dissociation energy D0 from ground electronic level

Usually no other electronic levels matter

1

qvib = ∑ e −nε 0 kT

= 1 + e −ε 0 kT

+ e −2ε 0 kT

+ e −3ε 0 kT

+" =

n 1 − e −ε 0 kT

Note we’ve set the zero of vibrational energy as the lowest vibrational level.

The zero-point vibrational energy has been included in qelec by using the

dissociation energy rather than the bottom of the electronic potential energy.

We have not treated qrot. Levels are NOT evenly spaced: εrot = J(J + 1)ε0,rot

For multiple species in chemical equilibrium, need to use Ni for each species and

use partial pressure values in pV term.

Gi = −RT ln (qi Ni ) = Gi ° + RT ln ( pi p ° )

⎛ qi Ni kT ⎞ ⎛ qi kT ⎞

Gi ° = −RT ln ⎜ ⎟ = −RT ln ⎜ ⎟

⎝ Ni p °V ⎠ ⎝ p °V ⎠

Assume all molecules have high vibrational frequencies ⇒ qvib ≈ 1 for all species

Translational & rotation: high-T limits

Assume similar rotational energies (depends on moments of inertia)

⇒ qtrans & qrot contributions are all equal

5.60 Spring 2008 Lecture #29 page 3

⎛q q ⎞

ΔGi ° = −RT ln ⎜ AC BD ⎟ = −RT ln K p

⎝ qAB qCD ⎠

qAC qBD e D AC 0, kT

e D BD0, kT

= e(

D0,AC +D0,BD −D0,AB −D0,CD ) kT

Kp = =

qAB qCD e D AB 0, kT D CD

e 0, kT

contribute equally.

NA molecules of A, NB molecules of B, NA + NB = N

and vibrational energy

If vibrational frequencies are the same, then only the difference in dissociation

energies is needed.

Q= ∑ i

e −Ei kT = ∑

Ei

Ω ( Ei ) e −Ei kT

microstates energies

N

N! N

N! N N

Q= ∑

Ei

Ω ( Ei ) e −Ei kT = ∑

NA = 0 NA !NB !

e ( NADA +NBDB ) kT

= ∑

NA = 0 NA !NB !

e( A ) e( B )

D kT A D kT B

energies

N

N!

∑N qANA qBNB = ( qA + qB ) = qAN (1 + s )

N

where s = qB qA = e (

N DB −DA ) kT

= = e ΔD0 kT

NA = 0 A !NB !

The binomial theorem gives a simple closed form for the sum.

N

Q = (1 + s ) = 1 + a1s + a2s2 + a3s3 + " + aN sN

5.60 Spring 2008 Lecture #29 page 4

Probability that the system has this energy is

p ( NA ) = aNA sNA Q

N

a1s + 2a2s2 + 3a3s3 + " + NaN sN s ⎛ ∂Q ⎞ ⎛ ∂ ln Q ⎞

NB = ∑ NBp ( NB ) = = ⎜ ⎟=

NB Q Q ⎝ ∂s ⎠ ⎝⎜ ∂ ln s ⎠⎟

and E = U = NB ΔD0

In general, low vibrational frequency favors a species since the levels are closely

For chemical reactions involving covalent bonds, the bond energies dominate

over entropy. But the treatment we’ve given could also be used for much more

Note that this treatment assumes no interactions between different unit cells.

Phase transitions between different crystalline phases may be easier to treat

then chemical reactions, because there is just one state at any temperature:

the crystal in phase α or the crystal in phase β.

Einstein model for crystalline phases α and β, frequencies να , νβ

Binding energy per atom: −εα, −εβ

Phase α Phase β

0

−εβ

−εα

You can predict the phase transition temperature based on a simple first

principles model.

Phase transition only occurs if the crystal with stronger binding energy, e.g. α

Note that this treatment assumes complete cooperativity: the crystal is either

all one or all the other phase. This gives rise to an abrupt T-dependence of the

equilibrium.

segments of helix or coil more stable than many short segments. (Similar for

Can also calculate solid-gas phase equilibria, i.e. vapor pressure over the crystal.

N

⎡⎛ 2πmkT ⎞3 2 ⎤ ⎛ ∂Ag ⎞

Q =q g N

trans N! = ⎢⎜ ⎟ V⎥ N! A = −kTln Q

g g

μ =⎜g

⎟

⎣⎢⎝ h

2

⎠ ⎦⎥ ⎝ ∂N ⎠T,V

32

⎛ 2πmkT ⎞

ln Q = Nln ⎜

g

⎟ V − Nln N + N

⎝ h

2

⎠

32 32

⎛ ∂ln Q g ⎞ ⎛ 2πmkT ⎞ ⎛ 2πmkT ⎞ V

⎜ ⎟ = ln ⎜ ⎟ V − ln N − 1 + 1 = ln ⎜ ⎟

⎝ h ⎝ h N

2 2

⎝ ∂N ⎠T,V ⎠ ⎠

32

⎛ 2πmkT ⎞ kT

μ g = −kTln ⎜ ⎟ (ideal gas)

⎝ h p

2

⎠

32 52

⎛ kT ⎞ ⎛ 2πm ⎞ (kT )

μ = −ε − 3kT ln ⎜

s g

⎟ = μ = −kT ln ⎜ 2 ⎟

⎝ hνE ⎠ ⎝ h ⎠ p

3 32

⎛ 2πm ⎞

32

(kT )5 2 ⎛ hνE ⎞ (2πm ) ν3E

ε = kT ln ⎜ 2 ⎟ ⎜ kT ⎟ = kT ln

(kT ) p

12

⎝ h ⎠ p ⎝ ⎠

32

(2πm ) ν3E

p=

(kT ) e ε kT

12

gives vapor pressure p(T) over the crystal! Strong binding energy or low T give

low pressure as expected. Low vibrational frequency also gives low p, since this

allows higher entropy in the crystal.

So you can calculate the p-T phase diagram that you described before in

macroscopic terms only.

- Memorization List (Mine)Uploaded bypringlek
- introduction to separation technologyUploaded byfaranimohamed
- Chapter 1~ Notes Sept 2015Uploaded byAlimah Azeli
- Equilibrium Practice Problems AnswersUploaded byJuniorGarcia
- Long Test 62009 Gas LawsUploaded byorganodiesel
- Oil & Gas Processing Engineering & ScienceUploaded byRandiRahmansyah
- (968)-chemistry-gyan-sutra-jee-main.pdfUploaded bySamien
- Liquids and Solids Test AnswersUploaded bymamazookeepr
- A Study of the Equilibrium between Ferric and Thiocyanate IonsUploaded byWombatNZ
- Physical properties of Sodium Niobate (NaNbO3) at different phase transitionsUploaded byInternational Journal of Engineering Inventions (IJEI)
- Vapor-Liquid Equilibrium of the CH4-CO2 System at Low TemperatureUploaded byClaudioTRodrigues
- 10.Phase Diagrams.pdfUploaded byMumpuniLuthfi
- AP '84 Multiple ChoiceUploaded byVignesh Babu
- Exp5-AutosavedUploaded byEllaine Tejada
- Free Energy of Formation of Al(OH)3Uploaded bysnakova
- cmc chapter 12Uploaded byapi-327761035
- CHE3165 Test 2 (2011).pdfUploaded byLahiru Perera
- kech107Uploaded byDharmender Dama
- 2006 Chem 1112Uploaded byHorizonAcademy
- 42_2_SAN FRANCISCO_04-97_0485Uploaded bynouimehidi
- 115 Sample Exam 1Uploaded bybebo4gpa
- 2-Propenesulfenic Acid Versus AllicinUploaded byInnurvi Diharningrum
- novec1230Uploaded byasifaliabid
- 0142Uploaded byLidka Jankowska
- discussin lleUploaded byssyerrina
- Ef 9014058Uploaded byMonica Roy
- Bernard_et_al_01(Biotechnol_Bioeng).pdfUploaded byC Donis
- Lix 973nsc Lv Ti Evh 0155Uploaded byCherezade Karine Saud Soto
- Ch10 PhasesUploaded byembargio
- Solid-liquid Metastable Equilibria in Quaternary System (NaCl+Na2CO3+Na2SO4+H2O) at 273.15 KUploaded byclintonc

- 41.basicUploaded bycaptainhass
- Taking Birth Control Pills to Fight AcneUploaded bycaptainhass
- Lecture 23Uploaded bycaptainhass
- Lecture 22Uploaded bycaptainhass
- 32.basicUploaded bycaptainhass
- 31.basicUploaded bycaptainhass
- Lecture 21Uploaded bycaptainhass
- Lecture 20Uploaded bycaptainhass
- Lecture 19Uploaded bycaptainhass
- Lecture 18Uploaded bycaptainhass
- Lecture 17Uploaded bycaptainhass
- Lecture 16Uploaded bycaptainhass
- Lecture 15Uploaded bycaptainhass
- Lecture 14Uploaded bycaptainhass
- Lecture 13Uploaded bycaptainhass
- Lecture 12Uploaded bycaptainhass
- Lecture 11Uploaded bycaptainhass
- Lecture 10Uploaded bycaptainhass
- Lecture 9Uploaded bycaptainhass
- Lecture 8Uploaded bycaptainhass
- Lecture 7Uploaded bycaptainhass
- Lecture 6Uploaded bycaptainhass
- Lecture 5Uploaded bycaptainhass
- Lecture 4Uploaded bycaptainhass
- Lecture 3Uploaded bycaptainhass
- Lecture 2Uploaded bycaptainhass
- Lecture 1Uploaded bycaptainhass
- Lecture 24Uploaded bycaptainhass
- L-44(GDR)(ET) ((EE)NPTEL)Uploaded byyashaswiyellapragada
- StartersUploaded bySri Jai Priya

- ARNU18GL2G4Uploaded byjulio
- NUMERICAL INVESTIGATION OF ELLIPTICAL AND TRIANGULAR PERFORATED FINS UNDER FORCED CONVECTIONUploaded byijsret
- Cooling Curve of Lauric Acid(1)Uploaded byRafael Castro
- Calorific Value of Liquid FuelUploaded byDeac SweetPsalmist Puni
- List of Chemical Engineering eBooksUploaded byVikram Narendra Tanna
- Piso Techo 2018 - YorkUploaded bydanvalgar
- Distillation TheoryUploaded byCJOR
- Integrated Design Initiative EKC 216 2016-2017Uploaded bySyamsul Rizal Abd Shukor
- Why+natural+ventilation+is+almost+always+stretched+to+its+functional+limits+HovalUploaded byJoshua Fernandez
- Phase Diagram Solid SolutionUploaded byFataa Naufal
- 5 Mass TransferUploaded bygeorgiadisg
- Chapter 5 ExerciseUploaded bySuriaraj Krishnan
- BEE Air ConditionersUploaded byRHL17
- MMU-AP0124HP-E - EVAPORADORA TOSHIBA - Cópia.pdfUploaded byCelso Brasil
- Enclosure and process coolingUploaded byFábio Seabra
- Design and Optimization of Water Cool Condenser for Central Air Conditioner.Uploaded byijripublishers
- PPD.pptxUploaded byPopoy Faj
- 10.Phase Diagrams.pdfUploaded byAbriyani Devi
- u05 Notes Part2 Bond Enthalpy Hess (1)Uploaded byKhondokar Tarakky
- Carrier Air Con 38QRR ManualUploaded byYorkist
- Step by Step Procedure to Do Shortcut Sizing for Air Cooled Heat Exchanger and Estimate Finned Area and Power RequiredUploaded bykarthick
- HVAC_Units_for_the_Replacement_of_wall_hung_units__11_15_2012.pdfUploaded bymecanico 2000
- Gibbs Homework SolutionsUploaded byAbu Farhoud
- TsonopoulosUploaded byCaique Ferreira
- retertUploaded byAnjith
- MCE 403-Natural and Forced ConvectionUploaded bynajmadeen
- Termotehnica part1Uploaded byCirstea Alexandru
- 3445601675138Uploaded byTon Phichit
- 1 基础知识.pptUploaded byGama Ajiyantono
- Thermostat - WikipediaUploaded byramthecharm_46098467