CHUONG 7 ảnh hưởng của dung môi lên tốc độ phản ứg PDF

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CHNGVII

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.

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