NewDirec)onsinHSPPart1Spli5ngδD

HSPiPDr.HiroshiYamamoto

2017.4.5

HSP50Conference2017

H.Yamamoto,personalHistory1967

1977

1987

1997

2007

Imarried

TookDr.degree1StGenera)onofiPhone

Myfirstprogrammableelectriccalculator.(Highschool2ndgrade)

ElementarySchoolfirstyear

MysecondPC(16bit)

HSPBirth

NeuralNetworkresearch

MOcalcula)on

Chemo-Informa)cs

G3Mac

2017：　HSP50

2008

HSPiP

PrimeNumber

CanyoudividePrimeNumber,2017?

Myanswerisalways“dependon”.2017=(44-9i)*(44+9i)Proper)esEs)ma)ondependonDataset.Hydrocarbons’Equa)onapplicabilityforXX.

Howwecanserve2017versionofHansenSolubilityParameters?

Dependonwhat?

CALCULATINGδD•  HOMOMORPHCONCEPT(ED=EFORSIMILARHYDROCARBON

•  CORRESPONDINGSTATETHEORY(CST)•  CSTFIGUREFOREDFOREACHOFALIPHATIC,CYCLOALIPHATIC,ORAROMATICSTRUCTUREEDversusVforTr=T298.15./TCRITICAL

FIGUREFOREDFORALIPHATICHYDROCARBONS

2otherchartsexistforCycloalkanesandAroma)cs.

Thereasonwhy3chartsexist

Wecan’tapplyChartMethodformorecomplicatedmolecules.

Aroma)c+

longAlkylchain

DifferentcurvesbetweenTrandHV

CALCULATINGδDinHSPiPδD = (nD-0.784)/0.0395 nD:Refrac)veIndex

About±1error

δP-FinalResultAdjustedfromTrialandErrorValues

BöpcherEqua)on,cal/cm3

( ) 2222

2 22

112108µ

εε

δ ++

−= D

DP n

nV

WhenconstantsnotavailableBeerbowerEqua)on,MPa½

δP=37.4(µ)/V½

LaterFunc)onalGroupContribu)ons

Evalua)onofδP

δP2 =12108V 2

ε −12ε + nD

2 nD2 + 2( )µ 2

IftheDipoleMoment(μ)isverysmallδPbecome0

μ=0 ε=2.52 δP=11.8

δP=37.4(µ)/V½

BöpcherEqua)on BeerbowerEqua)on

μ=0 δP=5.7symmetricalmoleculesProblemε=2.3

Comparisonof2Equa)ons

δP(Beerbower)=δP(Böpcher)+3.5

Forsymmetricalmolecules,Hansendeterminedthembyhandviaanalogy.

δH–FinalResult(Whatwaslevover)

EH=ET-ED-EPδH=(EH/V)

½

CHECKwherepossiblethat:

δT2=δ2

D+δ2

P+δ2

H

LaterFunc)onalGroupContribu)onsforEH

WeneedHeatofVaporiza)on@25℃(ET)beforecalcula)ngδH

CORRESPONDINGSTATETHEORY(CST)

Δ HvRTc = 7.08( 1- Tr ) + 10.95 ω (1-Tr)0.354 0.456

Δ Hv : Heat of VaporizationTr : Reduced Temperature (T / Tc)ω : Acentric factorR : Gas constant

Pitzer-Carruth-KobayashiMethod

Hv(Lit.) [KJ/mol]

Hv

(PCK

met

hod)

[

KJ/m

ol]

10

15

20

25

30

35

40

45

50

0 10 20 30 40 50 60

y = 4.0107 + 0.85516x R= 0.95632

IfwehaveTcandω,wecancalculateHv@25℃withPCKmethod

Func)onalGroupContribu)onMethod

MeCOO

Bu

Yamamoto

MolecularBreaktoFunc)onalGroupAlgorithm

Property=factori*FGiΣi=1

172Y-MBisimplementedinHSPiP

Proper)es:δD,δP,δH,AntoineA,B,CBP,MP,Tc,Pc,Vc,nD,MVolHv,logKow,logSsoon.

Y-MBEs)ma)on(Cri)calProper)es)

Y-MBEs)ma)on(EnvironmentalProper)es)

Y-MBEs)ma)on(Otherproper)es)

Developing2017versionofFunc)onalGroupContribu)onforHSP.

Me

COO

BuMe

COOH

Pr

NH

Bu

C4H8

C4H8

FG[δD,δP,δH]Vol

[12.9,0.7,0.1]28.85

[19.0,8.1,10.8]37.02

[15.2,0,0]94.25

[20.7,9.7,14.9]16.53

[14.7,0,0]72.2

[16.2,0,0]88.04[17.9,11.8,22.1]44.37

VolumeweightedHSPmixture

HSPmix=HSP1*φ1+HSP2*φ2

φ1+φ2

φ:VolumeFrac)on

Can’tdetermineδDcoefficientsforeachFunc)onalGroup!

ΣFGsFactor*FGsNumber+Const.

？

RareGases(NobleGases)

WeknowthatRareGasesbecomeliquidonlywiththeWeakVanDelWaals(VDW)Force.

Thereisverygoodcorrela)onbetweenMolecularWeightandBP

RareGases&FluorinatedCompounds

TheperfluorocompoundsbecomeliquidwithonlyweakVDWforce.

+Hydrocarbons

Evensamemolecularweight,hydrocarbonsneedmuchhigherboilingpoint.

WenamedthisbasecurveasδDvdw

ChangeAxes

δDvdw=(9.0463*MW0.5+28.512)/(MVol)0.5

δD2=δDvdw2+δDfg2Newdefini)on δDforFunc)onalGroup

SplitδDtoδDvdwandδDfg

δDvdw　

MVolMW

ΣFGsFactor*FGsNumber

δDFgδD　 +

InterceptforδDfg=0

2017versionofFunc)onalGroupContribu)onforHSP.

Me

COO

BuMe

COOH

Pr

NH

Bu

C4H8

C4H8

FG[(δDvdw,δDfg),δP,δH]Vol

[(11.8,7.5),0.7,0.1]28.85

[(14.5,15.2),8.1,10.8]37.02

[(10.0,12.3),0,0]94.25

[(15.6,17.8),9.7,14.9]16.53

[(10.7,14.0),0,0]72.2

[(10.3,14.0),0,0]88.04[(13.4,13.2),11.8,22.1]44.37

VolumeweightedHSPmixture

HSPmix=HSP1*φ1+HSP2*φ2

φ1+φ2

φ:VolumeFrac)on

dD=(dDvdw2+dDfg2)0.5

HSPFGparameters

SolventSizeEffect

n-Alkane’sDispersionTerm

Asthemoleculebecomeslarger,thesurfaceareadecreases.

δDvdwdecreasesasthesizebecomeslarger

SmallSolvent’sspecificNature

δD(δDvdw,δDfg)

Butylacetate15.6(9.93,12.03)

Methylpropylamine15.0(9.73,11.43)

16.3(9.06,13.49)Tridecanoicacid

15.5(13.34, 7.89)Water

0.1

0.8

0.5

5.4 4.9

7.0

NewHSPDistanceDistance1967={4.0*(δD1-δD2)2+(δP1-δP2)2+(δH1-δH2)2}0.5

Distance2017={(δDvdw1-δDvdw2)2+(δDfg1-δDfg2)2+(δP1-δP2)2+(δH1-δH2)2}0.5

Polymer88solvents

Polymer88examples

δDdetermina)onOfficialδDisnotalways“CorrectAnswer”.

Refrac)veIndexmethod YMBmethod PolarizabilityMethod

CrossCheckwithindependentmethod.

PolarizabilityMethodCalculated4,000+moleculeswithMOPAC2012andobtainedPolarizabilityvalues.

δD= ((Polarizability*1000-719.94)/ (0.3231*MVol))0.5

PolarizabilityMethodRefrac)veIndexmethod

Almostparallel

CrossCheckingforδDAmine Alcohol

Ester Ketone

δPdetermina)onOfficialδPisnotalways“CorrectAnswer”.

Dipolemomentmethod

YMBmethod

qEQChargeCalcula)onMethod

CrossCheckwithindependentmethod.

CrossCheckingforδPAmine Alcohol

Ester Ketone

TemperatureDependencyofHSP

dD

dP

dH Hv(T)

OriginalScheme

Hv(T)=FdD(T)+FdP(T)+FdH(T)

α:Coefficientofthermalexpansion

δD(T)=(FdD(T)/Mvol(T))0.5NewSchemeδP(T)=(FdP(T)/Mvol(T))0.5

δH(T)=(FdH(T)/Mvol(T))0.5

HowcanwedetermineFdD(T),FdP(T),FdH(T)　?

Needotherdataatdifferenttemperature.

CST

CST

CorrespondingStateTheory(CST)

Proper)es@T1mmHg/Proper)es@Tb→　Iden)cal

Verifica)onofTemperaturedependency

log1(mmHg)=0=A– B/(T1mmHg+C)log760(mmHg)=A– B/(TB+C)

MVol

＠T1mmHg ＠Tb

δD＠T1mmHg ＠Tb

128.2

94.1

90.3

150.3

110.8

105.0

0.85

0.85

0.86

16.6 13.6 1.22

17.1 14.1 1.22

16.5 13.6 1.21

/

/

/

/

/

/

=

=

=

=

=

=

logP(mmHg)=A– B/(T℃+C) AntoineParametersA,B,C

iden)cal

ConclusionBuiltFunc)onalGroupContribu)onMethod2017

NeedtosplitδDtermtoδDvdwandδDfg

BuiltnewHSPDistanceScheme2017{(δDvdw1-δDvdw2)2+(δDfg1-δDfg2)2+(δP1-δP2)2+(δH1-δH2)2}0.5

Withoutfactor4

SmallSolvent’sspecificNature

BuildingnewHSPOfficialValues2017CrossCheckingTemperaturedependentHSP

Thenewname?PleasethinkofnewnameofHSP!

InJapan,IusedHSP2Hansen-Hiroshi-StevenSolubilityParametersforPredic)on

EHSP:EnglishforHighSchoolPrepara)on,EnhancedHighSpeedProcessorEquineHealthStudiesProgram

Keepbrandiden)tyof“HSP”Networksearchable.Imageofnewandpowerfulness.

ExpandedHSP

HSP2

Y-Solvent2017

Y-Fit2017

SpecificJapaneseusersareusingnow

Theirfeedback,　　　revise.

Willreleasewithinthisyear(?)

🔁

CSTbasepoint

1mmHgT1mmHg

Revisepolicy1.  For14Kcompounds,Irankedeachmolecule.

Category1:IcheckedBarton’sBook“CRC,HandBookofofSolubilityParametersandothercohesionParameters”andselect206solvents.Category2:IcheckedHSPiPexamplesandselect83solventsCategory1-2solventsHSParewidelyusedandIdonotrevisetheseHSP.Category3:IcheckedDipper801databaseandextractSPvaluesandHeatofvaporiza)onat25℃.Forcategory3,IfOfficialtotHSPinHSPiParegoodagreement(415solvents)Category4:YMBcalcula)onresultoftotHSPandDippervaluesaregoodagreement,IimportYMBresult.(1325solvents)Category5:Verysimplemono-func)onalsolvents.(1572solvents)Category6:Halogenatedsolventsorotherimportant378solventsCategory7:Importantflavor561compoundsCategory8:Notabove.

1-2Ineverchange.OthersIrevised.

HSPtoHSP2　δD

HSPtoHSP2　δP

HSPtoHSP2　δH

InHSPiPMoreLargeFG

FGinterac)ons

≠ 3*CH3+C

version5.1?6.0?

MoreDynamicfeatureofMolecule

30GHz

Annmonia

Cyclohexane　Boat-ChairConforma)onchange

100,000)mespersecondatroomtemp.

ChangeVolumeInducedChargeKillHydrogenBond

ΔδTΔδPΔδH

EvenHydrocarbonshaveδDfg

FluorocarbonshavelipleδDfg

EquivalentAlkaneCarbonNumber(EACN)

EACN=7.9 δDvdw=8.9

EACN=8.0 δDvdw=9.1

SomeoftheMetalFluoridesbecomeLiquidwithonlyVDWforce

FromlevNF3,SiF4,PF5,SF6,AsF5,SeF6,WF6,ReF6,OsF6,IrF6,NpF6,UF6

PF5

PF3

SF6

SF4

TheseMetalFluoridesmayhavenoCataly)cac)vity