maxwell relations

Attribution Non-Commercial (BY-NC)

80 views

maxwell relations

Attribution Non-Commercial (BY-NC)

- NIOS 12 Chemistry Syllabus
- Maxwell Relations
- Jee 2014 Booklet3 Hwt Chemical Equilibrium
- P.H. Groggins Unit Processes in Organic Synthesis.pdf
- Chemical Equilibrium 3
- Science in Uncertainty
- chemistry journal 3.pdf
- Chemical Equilibrium Type 1
- Lecture 2- BioEnergetics
- 377869 Equilibrium and Pressure Kp Topic Exploration Pack
- Thermodynamics of Enzyme
- Chemical Equilibrium
- Thermo Sheet7 New
- Melaka Trial Chemistry 2011 P1
- CO2 Corrosion
- CHM12-3 Syllabus
- CHM 152 Final Exam Review 1 Spring 2012 NEW KEY
- Text
- Phase Diagram
- Lec 02 Thermo Review A

You are on page 1of 17

U T = V T dU = PdV + TdS dU dS = P + T dV dV U S P = P + T = P + T VT V T TV dU = CV dT + T P dV = TdS PdV

What is H ? PT

Determination of CP -CV

H C P CV = CV TP ( PV ) U C P CV = + CV TP T P P V T V C P CV = C V + T P + P CV T P T V T P T P P V C P CV = T = T TV T P CP CV = VT

2

Temperature Dependence of the Gibbs Free Energy Gm

A B

dG m = Vm dP Sm dT Gm = Sm T P

solid

liquid Tm

gas Tb T

At point A the solid is in equilibrium with the liquid Gm(S)= Gm(L) At point B the liquid is in equilibrium with the vapor Gm(L)= Gm(V)

Gm Hm Gm = Sm = T T P Gm Gm H m = T T T P Gm H m 1 Gm 2 = 2 T T P T T Gm T H m = T T2 P G T H = 2 T T P

dG m = Vm dP Gm = Vm ( P)dP

Pi Pf

Pf G m = RT ln Pi

At low P, Vm is independent of P

Gm = Vm Pf Pi

G m = Vm ( P )dP

Pi

Pf

Phase Diagram: P = f(V,T) Coexistence Curves Triple Point Critical Point Location of Phase Boundaries:

Gm = Vm P T

if Vm(L) > Vm (S) then Tm increases with Pressure (general) if Vm (L) < Vm (S) then Tm decreases with increasing pressure (water, etc..)

Two phases and are in equilibrium at temperature T and pressure P, if Gm (P,T) = Gm (P,T) Let us change P by dP and find out what is the corresponding dT required to preserve the equilibrium between the two phases. Changes of T by dT and P by dP lead to a change of G by dG d Gm = -Sm dT + Vm dP for the phase and d Gm = -Sm dT + Vm dP for the phase To preserve equilibrium conditions, Gm + d Gm = Gm + d Gm which implies d Gm = -Sm dT + Vm dP = d Gm = -Sm dT + Vm dP (Sm -Sm ) dT = (Vm - Vm ) dP

dP S H = = dT V TV

H fus (T*, P *) T dP H fus (T,P ) = P = P* + ln V fus (T*, P *) T * dT TVfus ( T, P)

if Hfus and Vfus can be assumed independent of T and P Liquid - Vapor Equilibrium

dP H vap ( T, P ) H vap (T, P ) H vap (T, P ) = = TRT dT TVvap (T, P) TVvap (T, P) P dP H vap (T , P) dT = R P T2 1 P H vap 1 ln = P * T T * R

dP H sub (T, P) H sub (T, P) H sub ( T, P) = = TRT dT TVsub ( T, P ) TVsub (T, P) P dP H sub ( T, P) dT = P R T2 P H sub = ln P * R 1 1 T T *

if Hsub can be assumed independent of T and P Close to the triple point Hsub = Hfus + Hvap Because H is a State Function

X XJ = Partial molar value of extensive property X n J n ,P,T is an Intensive property of a component in a mixture I

G = J = n J n ,P,T I

+ RT ln a ( J J

Standard State (P = 1 bar) Ideal Binary A-B Liquid Solution: Raoults Law PA = xA PA* where aA = xA = nA / (nA + nB) mole fraction of A Gmix = (nA+nB)RT(xA ln(xA) + xB ln(xB)) Hmix = 0 Vmix = 0 Smix = - (nA+nB) R (xA ln(xA) + xB ln(xB))

Phase Diagrams

Gibbs Rule of Phase: The number of independent intensive state variables necessary to fully define the state of a system is called the variance of the system(or the # of degrees of freedom) and is given by F = C - P + 2 where C = # of independent constituents (# of species if no reaction) P = # of phases 2 accounts for T and P F = 0 the system is invariant (triple point) F = 1 the system is monovariant (L/S, L/V, S/V coexistence) F = 2 the system is bivariant (single phase & single component) F = 3 the system is trivariant (single phase & 2 components)

Chemical Equilibrium

Consider the reaction 2A + 3B C + 2D If we define the extent of reaction by , when the reaction advances by d , the amount of reactants changes by: dnA = -2 d dnB = -3 d In general, for a reaction written as dnC = d J J = 0, then dnJ = J d dnD = 2 d At constant temperature and pressure: dG = A dnA + B dnB + C dnC + D dnD dG = (- 2A - 3B + C + 2D ) d In general dG = J dnJ = (J J) d

G RG = P,T

G = J = n J n ,P,T I

J

+ RT ln(a J )

where aJ is PJ/P or fJ/P for gases and unity for pure liquid and pure solids. RG = RG +RT lnQ

a1 a 2

D Q= C 2 a 3 aA B

In general, RG = J J

J and Q = a J J

At equilibrium, RG = 0

K = aJJ J eq

a1 a 2 K = C D a3 a2 B A eq

In general,

RT ln K = - RG and K can be calculated at a given temperature from the free energies of formation for each of the reactants and products

R G = J f G ( J )

J

Standard Gibbs Free Energy of Formation of 1 mole of Substance J at temperature T and 1 bar found in thermodynamic tables.

Pressure Dependence: K depends on G(T) and T and NOT on pressure. Temperature Dependence:

G T H = T T2 P G R T R H = T T2 P

R H = J f H ( J)

J

RH ln K = T P RT 2

If the standard reaction enthalpy can be calculated at T* (generally at 298K) and if the molar heat capacity of reactants and products is known as a function of temperature, an expression for the temperature dependence of the reaction enthalpy can be obtained. Then the equilibrium constant can be calculated at any temperature (T1) in terms of the equilibrium constant at T* (the latter being calculated from the standard free energy of formation of products and reactants).

1 T1 R H (T ) dT d ln K = 2 R T* T K (T*) R H (T ) = R H

J K ( T1)

(T *) + R CP (T )dT

T*

R C P (T ) = J Cp,m ( J, T )

- NIOS 12 Chemistry SyllabusUploaded byTarak Bhardwaj
- Maxwell RelationsUploaded byRaghav Agrawal
- Jee 2014 Booklet3 Hwt Chemical EquilibriumUploaded byvarunkohliin
- P.H. Groggins Unit Processes in Organic Synthesis.pdfUploaded bySintong Leonardo Situngkir
- Chemical Equilibrium 3Uploaded byNoEr IKu Iwed
- Science in UncertaintyUploaded byManjunathRamu
- chemistry journal 3.pdfUploaded byPuspa Riani Widiyanti
- Chemical Equilibrium Type 1Uploaded byNeeraj Misra
- Lecture 2- BioEnergeticsUploaded byMkhahlelwa
- 377869 Equilibrium and Pressure Kp Topic Exploration PackUploaded byAnonymous UYGc2zA
- Thermodynamics of EnzymeUploaded byQrichaud
- Chemical EquilibriumUploaded bySachin Kumar
- Thermo Sheet7 NewUploaded byRodney Salazar
- Melaka Trial Chemistry 2011 P1Uploaded byChong Chin Siong
- CO2 CorrosionUploaded byShie Othong
- CHM12-3 SyllabusUploaded byPaul Maynard
- CHM 152 Final Exam Review 1 Spring 2012 NEW KEYUploaded byCaguioa Mark Anthony G.
- TextUploaded bySchwanSty
- Phase DiagramUploaded bymohanadymt
- Lec 02 Thermo Review AUploaded byBarry Head
- Kumar 1996Uploaded byAndres Palchucan
- Reactors DesignUploaded byjoaquin
- Chemical Equilibrium in a Liquid PhaseUploaded byKuo Sarong
- EquilibriumUploaded bybharath
- vle dataUploaded byAravind Kumar
- scipharm-71-00075.pdfUploaded bySumedh K
- Lecture 3 Clausius InequalityUploaded byBhuwanesh Kumar
- chapter 3Uploaded byMohan Rao Damacharla
- equilibrium 2.pptUploaded byVon Valentine Mhute
- Chemical_Equilibrium.pdfUploaded byIvon Adolfo

- 01496391003652783Uploaded byArun Ebenezer
- 9. henry 's law.pdfUploaded byArun Ebenezer
- allemande.pdfUploaded byArun Ebenezer
- allemande.pdfUploaded byArun Ebenezer
- Chemical Composition and Surface Property of KaolinsUploaded byArun Ebenezer
- Chapter 3 CalibrationUploaded byArun Ebenezer
- Detection principles and development of microfluidic sensors.pdfUploaded byArun Ebenezer
- Liquid Vapor e QuilUploaded byFrancisco Martinez
- High-Pressure HighTemperature Microreactors for Nanostructure SynthesisUploaded byArun Ebenezer
- Advanced Drug DeliveryUploaded byArun Ebenezer
- formaldehydeUploaded byWerner Janssens
- Microfluidics Its Impact on Drug DiscoveryUploaded byArun Ebenezer
- Mass Transfer Dr AurobaUploaded byNagwa Mansy
- Fuel Processing of Diesel and Kerosene for Auxiliary Power UnitUploaded byArun Ebenezer
- Integration of Rational FractionsUploaded byJanesha
- Modeling of the Oxygen Transfer in the Respiratory ProcessUploaded byArun Ebenezer
- chap1-1Uploaded byFelix Ws
- Diffusion, Blood Oxygen, Co2 EtcUploaded byArun Ebenezer
- chapter1,2,3-1Uploaded byArun Ebenezer
- Capillary ElectrophoresisUploaded byArun Ebenezer
- fc_10_2_021003Uploaded byArun Ebenezer
- Catalytic Features of Rh and Ni Supported Catalysts in the Steam ReformingUploaded byArun Ebenezer
- Nitrogen Based Zinc Oxide Thin Films Biosensor for Determination of Uric AcidUploaded byArun Ebenezer
- Real-time in Vivo Uric Acid Biosensor SystemUploaded byArun Ebenezer
- Artigo Rosa Applied Clay Science.Uploaded byArun Ebenezer
- Characterization, Beneficiation and Utilization of a Kaolinite ClayUploaded byArun Ebenezer
- White SilicaUploaded byArun Ebenezer
- A review of the beneficiation of rare earth element bearing minerals.pdfUploaded byArun Ebenezer
- 10-1-291Uploaded bySudhir Singh Parihar

- Behaviour of Phenolphtalein in Strongly Basic MediaUploaded byNurul Shivani
- 6.2Uploaded byJitendra Maurya
- VEDST003 - Shell and Tube Heat Exchanger Specification SheetUploaded byyuganter
- petroleum reservoir simulation basics - L1Uploaded byshanecarl
- Critical diameter of insulationUploaded bySemihBaşkale
- 43 Apparent Molar Volume, Isentropic Compressibility and Conductivity of Di-sodium Hydrogen Phosphate in Water and in Aqueous Solutions of 1-PropanolUploaded byMarcoEnriqueRamosCastillo
- eu3c6 By Adel KhamisUploaded byAdel Khamis
- RefrigerationUploaded byOgenioja
- Emp Formula Zinc Chloride Web 01-02 (2)Uploaded byMohd Imran Noordin
- Molecular DiffusionUploaded byNagwa Mansy
- Gas SeparationUploaded byKatherine Tasan
- 03 External ConvectionUploaded byalagar krishna kumar
- Expt. 7 ATQUploaded byJunko Tsukuda
- A.1.2.3Uploaded byNadole Quist
- Methylamines Synthesis_A ReviewUploaded bysatishchemeng
- Abstract and Introduction for Master ThesisUploaded byRaju Patil
- (energy) Solar drying.pdfUploaded byJuan Peralta
- History of AtomUploaded byohsureee
- StatUploaded byAhmedAlhosani
- Pre-Heater of Nat GasUploaded byEstelle Diane Jose
- Ion Selective ElectrodesUploaded byrk_gummaluri5334
- 14 - Oxidation Numbers NG 2011Uploaded byHasantha Perera
- AspirinUploaded byMeagan Mahangoo
- Chemistry.docxUploaded byheena
- Lecture 1 - Basics of ThermodynamicsUploaded byMuhammadHamza
- properties-of-pure-substance-compatibility-mode1.pdfUploaded byMariela030
- 1-Psychrometry and ProcessesUploaded byWaleed Tahawy
- The Basic Knowledge About Gas HydrateUploaded byssaurabh574
- Equilibrio L-L Para Extracción de MMA (MeOH - Agua - Metanol - Hexano)Uploaded byPau Zalazar
- Steam Jet Refrigeration System and ICe RefrigerationUploaded by01parth