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CHUONG 7 ảnh hưởng của dung môi lên tốc độ phản ứg PDF
CHUONG 7 ảnh hưởng của dung môi lên tốc độ phản ứg PDF
NHHNGCADUNGMILNTCPHNNG
I.PDNGCCQUYLUTCATHUYTVACHMHOTNG
VPHCHOTNGCHOPHNNGTRONGDUNGDCH.
II.SSOLVATHA.
1.Lcgiaccphnt
2.Cutrcchtlng
3.SSolvathaphnttrunghavion
4.MuSolvathatnhin.
III.PHNNGCAPHNTTRUNGHADINRAQUATRNG
THICHUYNTIPKHNGPHNCC.
IV.NHHNGCAPHNCCLNTCPHNNGPHN
CC.
1.Phnngcaphnttrunghodinraquatrngthichuyntip
chophncc
2.Phnnggiaccion
3.Phnnggiaionvphnttrungha.
V.NHHNGCASOLVATHARINGLNTCPHNNG
1.nhhngcaSolvathaionlntcphnngphncc
2.Sinlycaion,Solvalhacccationvtcphnng
CHNGVII
NHHNGCADUNGMILNTCPHNNG
Tuytiasphnnglphnngcahpchthucdinratrongdungdch.Do
vy,nghincunhhngcadungmilntcphnngcnghalthuytcngnh
thctinquantrng.
phalngphntchtphnngvdungmitipxcvinhaumtcchkhngkht,
lctngtctnghgiachngtngiln.Bnchtcacclcnyrtkhcnhauv
baogm:lcphntn(khuchtn)London,llctngtcgiaccmmyelectron
caccphntringrquatngtctnhinlcCulongcaccphntphncc,hoc
bphncctoralinkthydrovcclinkthahcringrkhc.Chonnay,chac
khnngmtmtcchycctngtcny.Vvy,chngtachcmu(mhnh)v
sphthucbnthcnghimtcschovicgiinghcccphnngdinratrong
dungdch.
Nidungcbnvnhhngcadungmilntcphnnggmmyvnsau:
I.pdngccquylutcathuytvachmhotngvphchotngchophn
ngtrongdungdch.
II.Ssolvatha.
III.Phnngcaphnttrunghadinraquatrngthichuyntipkhngphn
cc.
IV.nhhngcaphncclntcphnngphncc.
V.nhhngcasolvatharinglntcphnng.
I.PDNGCCQUYLUTCATHUYTVACHMHOTNGV
PHCHOTNGCHOPHNNGTRONGDUNGDCH
(Xemmc5.3.10).
II.SSOLVATHO
1Lcgiaccphnt TOP
HintngsolvathagyradotcdngcalcVanderVaals.Lcnycngungc
calchatr,csinhradotngtcgiaelectronvhtnhnnguynttrongccphn
t,cmtbngphngphpchclngt.
a)Lcsinhradotngtcgiaccnguyntmangintchviphnt,cngnh
giaccphntcintchbtixng(phntlngcc).Trongsgnngcthgii
thchbnchtcalcbngtngtctnhin.Lclngccny(tngtcionlng
cc,lngcclngcc)lmthmscaintchionvmomenlngcccaphn
t,lngccgimkhitngsphnt.
b)Tngtcgiaccphntkhngphncchocphntphnccbchimot
intchviccionhocphntcmomenlngcc.Cngcthmtlcnybngmu
tnhin.Lcnyphthucvophncccaphntvintch,momenlngccca
ccphntcmng.
c)Lckhuchtn(hoclcLondon)sinhradotngtcgiaccnguyntvphn
tbtcotintchcmomenlngccbn.Cthgiithchlcnyhnhthnhdokt
qucaschuynngcaccelectrontrongnguyntvphnt,vcmtnhmt
hmscaphnccvthionhaphnt.Tngtcnylitvotngtcgiacc
phnt.Lctngtcgiaccphntloinyllcyuditcdngcankhngdn
nshnhthnhlinktgiaccphnt.Ngcli,lctngtcgiaccionhoccc
phntlngccctrsln.Ngoira,cnclctngtccbit.llclinkt
hydr,linktchonhn.
d)Lclinkthydro:Lcgyrashnhthnhlinkthydrogiahaiphntcho,
nhn.Vd,linktgiaphntaxitcacboxylvihpchtcnhmOHthaxitlphnt
(cht)cho,cnrulchtnhn.Linktnyllinktyu,nnglnglinkttrong
khong48Kcal/mol.Khnngtoralinkthydroldotnhchtctrngcaccdung
midbprotonhanh:nc,ancol,amit,axitcacboxylvhpchtkhc.
e)Tngtcchonhnelectron
Linktchonhnelectronxyragiaccphntccimcho,nhnelectron.
Phntchaelectron ,cthionhathpctnhchtchoelectron,vd,baz
Levis,cnphntcorbitalbntrongtrngkhng,cilchahccaolchtnhn
electron.VdaxitLevis.
Vd,linkttrongphcchtllinktchonhn.
2Cutrcchtlng TOP
Lctngtcgiaccphntcacngmtdungmictrsskhcnhau,ph
thucvocutrccaphnt.Cutrcchtlngldoktqutngtccalcny.l
lckhuchtn,khngnhhng,b.Vd,trongtrnghpdotngtccadungmi
khngphncc,hocrttphncc,thucchtlngccutrcnhnhtdngbn.
Cndotngtccaccphntphncc,hocbphnccmnh,bprotonhamnhnh
tngtckhuchtnmnh,hoctngtcdipoldipolcnhhng,thcngthuc
dngbncachtlng.
Vdnhhydrocacbonnolchtlngthnht,chtlngdngthhainhnc,
ancol.chtlngnytntilinktcuhydro:
Nclchtlngcbit,binlyt,cthtoralinktcuhydrodngtdin:
3Ssolvathaphnttrunghavion TOP
Khichuynchttantphakhvomitrnglng,ccphntcachttantngtc
viphntdungmi,dolmtnglctngtctnghgiaccphntdungmi.
Chttancnglmthayilctngtcgiaccphntdungmivcutrccan.C
haiyutnylmthayihmnhitngtiuchuncaccchtchokhichuyntpha
khvodungdch,tcllmthayicchmnhitngcassolvatha.Nuchch
tidungdchlongltng,trongkhngctngtcgiaccphntchttanvinhau,
thssolvathagnlinviviclmgimthnngvlmtngsnhhngcachttan
vdungmi,iudnnlmgim
Sthayitrngyrasthayibinthinentanpitdosolvatha:
ilngth(1),biuthtngtctnghgiachttanvidungmi,sdngi
lngnydgiithchvtholunhn.
Cthxcnhcgitrbngscaccilngtrnbngccphngphpkhc
nhau,vd,davootan.
Cnlu,entanpitdocashydrathalnhtrongtrnghpcahpchtnhm
knc,chngkhngthtoracuhydrokhicsthamgiacancvvthlmhthp
dngnycalinktgiaccphntnc.Dovy,mentropivnhithydrathacgitr
ln,chaigitrvanium,vthnhhngcanln: cbtrmtphn.
Stngnhanhentanpiventropikhihatanhpchttrunghavonccthcgii
thchnhsau:ccchtnylmtngsinlymtcchrrtkhinbbaobcbinc.S
liuthcnghimchothytcdngnygimxung,khitngkchthcphnt,tuynhin,
nguynnhncatcdngnychaclmsngt.
Ngcli,chtinlykncionbsolvathatrongmitrngnc.Mc
hydrattngkhigimkchthc.
Anionbsolvathatrongmitrngncmnhhncationtngngvkch
thc.
Tsliuthcnghimcnchothy:entropihydrathagimkhngangk,nhng
gimnhiuiviion ,thmchgimnhiuhnctrnghp
chtkhnginly,dotngtctnghgiaccionvphntnclmtngsnh
hngcachngvdolmgimmnhentropi.iucbiudinbngstnti
lpkhquynsolvathabaoquanhionn.Ccphntdungmibaobcgnnht(trc
tip)ionsolvathatoralpscp.
Tthcnghimchothy,ionsbsolvathartmnhngaycdungmikhngnc
soviphnttrungha.Cskhcnhaurrttrongtngtcsolvathacadungmi
protonha(vd,nc,metanol)vkhngprotonhavidungmiphncc(vd,
acetonitryl,dimetylformamid).Dungmiprotonhalchtchotronglinkthydro,biv
chngcthbsolvathamnh.Anionlchtnhntronglinktny,dungmikhng
protonhaskhngckhnngtoralinkthydro.Skhcnhaunycngrrttrong
trnghpanionnhvbhthp,khikchthccachngtng.
Hpchthuctrunghabsolvathamnhhntrongdungmihucsovitrong
nc.iunichungchxyraivitrnghpcaccphntln(vd
nitrobenzen).Ncvaitrtngtnhtrongtrnghpionhucln.
4Musolvathatnhin TOP
III.PHNNGCAPHNTTRUNGHODINRAQUATRNG
THICHUYNTIPKHNGPHNCC
Trongtrnghpnyssolvathachtthamgiaphnngkhngkhcnhiusovis
solvathatrongtrngthichuyntip.Do,khngcnhhngcadungmilntc
phnng.
IV.NHHNGCAPHNCCLNTCPHNNGPHN
CC
Skhcnhaunhiuvgitrentropitdocassolvathaphntkhngphncc
trungha,cngnhphnt,ionphncc.lnguynnhngynhhngrrtlntc
phnngivinhngphnngctrngthichuyntipvtrngthibanukhc
nhaunhiuvphncc.
1Phnngcaphnttrunghadinraquatrngthichuyntipphn
TOP
cc
2Phnnggiaccion TOP
Vdvloiphnngny:
NH4(+)+OCN()(NH2CONH2(Ur)
3Phnnggiaionvphnttrungha TOP
Phnngcaionviphnttrunghadinraquatrngthichuyntipcintch
hiudngnhtrngthiu,khichtilctnhinivihshotcaphchot
ng,nubquanhhngcadungmilnhshotcaphnttrungha,thuc:
Nutrngthichuyntipcphncccaohnchtphnng,thtcphnng
tngkhitnghngsinmitronghnhpdungmi.ngbiudinkhngphilun
lunlngthng.Cthlccdngngcongkhcnhau,iviphnngtronghn
hpdungmikhcnhauvnhnclchcdukhcnhau.Gyrassailchtrnl
docsnginhamhnhcoidungminhhinmilintc.
Mtsvdloiphnngny:
OH()+CH3I [OHd...CH3...Id]*CH3OH+I()
V.NHHNGCASOLVATHORINGLNTCPHNNG
Cthgiithchnhhngcadungmilnhottnhcachttan.Dungmitc
Cthgiithchnhhngcadungmilnhottnhcachttan.Dungmitc
dngkhngchnhlmitrnginmilintctoraintchhaythpphnt,m
cnthamgiavotngtcgiaccphntringrgiaccphntdungmivphnt
chttanlmchophntchttannnhmcnhtnh.ltngtcringrch
yusau:
a)Solvathacation(hocintchm)qualinkthydrochnhthnhnhsc
mtcadungmiprotonhanhnc,ancol,phenol,axitcacboxylaminaxit(nhmOH,
NH).
b)Solvathacation(hnhthnhphcchonhn)vidungmimphntcanc
nguyntchacpelectrontdo,vdnhoxy,nit.iuxyrakhngchivi
dungmikhngprotonhanhete,aceton,axitdisunfonic,dimetylfomamidvcdung
miprotonha.
c)Solvathaphnttrunghatoracutrccuhydro(tngtcchonhn).
1nhhngcassolvathaanionlntcphnngphncc TOP
Khnngcadungmiivissolvathaanionintchmquacuhydrothng
quytnhnhhngcanlntcphnngphncc.Nhsolvathaaniontrnnn
nh,hathcangim,dohottnhbgim.
Trongdungmiphncckhngprotonhakhngthhnhthnhlinkthydro,anion
bsolvathamckhngnhiu.Ngcli,trongdungmiprotonha,anionnhb,b
solvathamnhqualinkthydro.
2Sinlycaion,solvathacationvtcphnng TOP
Siemioczenko,Bjerrumchorng,chtingiimnhkhngnhtthitinlymtcch
hontontrthnhiontdobsolvatha,mcnioncintchngcducthbin
lygyradolchttnhintoraionkp,ba,lcthitlpcnbnggiacpionin
ly:
BitpchngVII
3.Chobitnguynnhngyrasthayitcphnngtrongdungdch.