Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina...
Transcript of Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina...
![Page 1: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/1.jpg)
Lecture8ChangesofStateAndColligativeProperties
![Page 2: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/2.jpg)
“PHASE”(P)
Astateofmatterthatisuniformthroughout,notonlyinchemicalcompositionbutalsoinphysicalstate.
“NUMBEROFCOMPONENTS”(C)
Theminimumnumberofindependentspeciesnecessarytodefinethecompositionofallphasespresentinthesystem.
![Page 3: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/3.jpg)
Thechemicalpotentialofasampleisuniformwhenitisatequilibrium,regardlessofthenumberofphases.
TTbTm
µ Solid
Liquid
Gas
Solidstable Liquidstable Gasstable
S(s)<S(l)<<S(g)
µs=µℓ
µℓ=µg
![Page 4: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/4.jpg)
ONE-COMPONENTSYSTEMS
![Page 5: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/5.jpg)
PHASEDIAGRAMSp,T-intensiveproperties
T
p
Liquidstable
Vapourstable
Vapourstable
Tc
Solidstable
Howdowedeterminetheboundariesbetweendifferentphases?
µα=µβ
Answer:from
![Page 6: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/6.jpg)
WechangepandTinfinitesimallybydpanddT:
CLAPEYRONEQUATION
Slopeofthep(T)boundarycurvesT
p
s g
l
![Page 7: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/7.jpg)
Solid-liquidboundary(melting)
>0
ifΔVm>0(common),dp/dT>0
Small:largeslope,steepcurve
ifΔVm<0(rare),dp/dT<0
T
p
sg
l
T
p
s g
l
![Page 8: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/8.jpg)
Liquid-vapourboundary(evaporation)
large:theslopeissmallerthanforthesolid-liquidboundarywherethetwocurvesmeet.
T
p
sg
l
T1
T2>T1gp2>p1
ΔVm=Vm(g)-Vm(l)issmallerathigherp!
![Page 9: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/9.jpg)
CLAUSIUS-CLAPEYRONEQUATION
![Page 10: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/10.jpg)
(e) (d) (c) (b) (a)
CLAUSIUS-CLAPEYRONEQUATION,integralform
![Page 11: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/11.jpg)
Solid-vapourboundary(sublimation)
T
p
s g
l
wheretheboundariesmeet
![Page 12: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/12.jpg)
Themeetingpointofthethreeboundaries:THETRIPLEPOINT
T
p
s
g
l
![Page 13: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/13.jpg)
THEPHASERULE
TheVARIANCE(i.e.thenumberofdegreesoffreedomofasystem)isgivenby:
F=C-P+2C-numberofcomponentsP-numberofphases2-pandT
![Page 14: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/14.jpg)
Forasinglecomponent:F=1-P+2=3-P
T
p
sg
l
F=2F=1
F=0
F=2:thesinglephaseispreservedwhenbothTandparechangedindependently.F=1:Tandpcannotbechangedindependentlytopreservetheequilibriumbetweentwophases.
F = 0: the triple point is out of our control - it depends on thepropertiesofthesystemanditoccursatasingle,welldefined(p,T)coupleofvalues.
![Page 15: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/15.jpg)
PhaseDiagramsCarbon dioxide
![Page 16: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/16.jpg)
SupercriticalFluids
![Page 17: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/17.jpg)
TheCriticalPoint
![Page 18: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/18.jpg)
CriticalTemperaturesandPressures
![Page 19: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/19.jpg)
Water
![Page 20: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/20.jpg)
Water
![Page 21: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/21.jpg)
Iodine
![Page 22: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/22.jpg)
TWO-COMPONENTSSYSTEMS
(a)Twovolatilecomponents
![Page 23: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/23.jpg)
ConsideramixtureoftwovolatileliquidsAandBAtequilibrium:
Wedenotepuresubstanceswith*.ForpureA:ForAinthemixture:
VapourPressureofpureA
VPofAinthemixture
![Page 24: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/24.jpg)
Formixturesofcloselyrelatedliquids(“idealsolutions”):
Raoult’sLaw T=const.
![Page 25: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/25.jpg)
ExampleofamixturecloselyobeyingRaoult’sLaw:
T=const.
![Page 26: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/26.jpg)
DeviationsfromRaoult’sLaw
TheDILUTESOLUTEobeysHENRY’SLAW:
TheALMOSTPURESOLVENTobeysRAOULT’SLAW
T=const.
![Page 27: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/27.jpg)
NegativeandpositivedeviationsfromRaoult’sLaw
![Page 28: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/28.jpg)
Example1:negativedeviationsfromRaoult’sLaw
![Page 29: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/29.jpg)
Example2:positivedeviationsfromRaoult’sLaw
![Page 30: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/30.jpg)
Thevapourisricherinthemorevolatilecomponent
![Page 31: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/31.jpg)
VapourPressureDiagrams
Thevapourisricherinthemorevolatilecomponent
T=const. T=const.
![Page 32: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/32.jpg)
VapourPressureDiagrams:DistillationatT=const.
Lever’sRule:
![Page 33: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/33.jpg)
Distillationatp=const.Temperature-CompositionDiagrams
ForIdealSolutions:FractionalDistillation
Vapour
Liquid
T=const
p=const
![Page 34: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/34.jpg)
![Page 35: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/35.jpg)
Distillationatp=const.Temperature-CompositionDiagramsForNon-IdealSolutions.Azeotropes.
Maximum-boilingazeotrope Minimum-boilingazeotrope
![Page 36: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/36.jpg)
H2O HClMolefractionofHCl
108.58°C
-111°C
�HCl=0.111
100°C
MolefractionofH2O H2OEthanol
78.4°C
100°C
�H2O=0.096
78.17°C
Twoexamples
![Page 37: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/37.jpg)
TWO-COMPONENTSSYSTEMS
(b)Anon-volatilesolute
COLLIGATIVEPROPERTIES
![Page 38: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/38.jpg)
COLLIGATIVEPROPERTIESarethosepropertieswhichdependonlyontheNUMBERofsoluteparticlespresent,
notontheirIDENTITY.
- VapourPressureDecrease- BoilingPointElevation- FreezingPointDepression- OsmoticPressure
![Page 39: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/39.jpg)
VAPOURPRESSUREDECREASE
non-volatilesolute,doesnotdissociate
p<p*
TherelativedecreaseofthesolventVPisequaltothesolutemolefraction
![Page 40: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/40.jpg)
![Page 41: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/41.jpg)
![Page 42: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/42.jpg)
Whatifthesoluteisastrongelectrolite?
![Page 43: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/43.jpg)
Whatifthesoluteisaweakelectrolite?
I
V
E
van’tHoffCoefficient
![Page 44: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/44.jpg)
GENERALEQUATIONFORVAPOURPRESSUREDECREASE
van’tHoffCoefficient
χ solvent =
nsolvent
nsolvent + i × nsolute
= PP *
![Page 45: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/45.jpg)
BOILINGPOINTELEVATIONANDFREEZINGPOINTDEPRESSION
![Page 46: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/46.jpg)
m-molality[m]=mol/kg
![Page 47: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/47.jpg)
Determinationofapproximatemolecularmasses
![Page 48: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/48.jpg)
OSMOTICPRESSURE
![Page 49: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/49.jpg)
![Page 50: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/50.jpg)
![Page 51: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/51.jpg)
Determinationofapproximatemolecularmasses
HighPforsmallconcentrationsÞ Verysensitive
Þ MMofmacromolecules
![Page 52: Lecture n. 8 farmacia · 2019. 1. 17. · Lecture n. 8_farmacia.pptx Author: maurizio_retina Created Date: 1/17/2019 7:15:29 AM ...](https://reader033.fdocuments.in/reader033/viewer/2022061003/60b223aced327e79cd52765a/html5/thumbnails/52.jpg)
INVERSEOSMOSIS