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CHNG VII

NH HNG CA DUNG MI LN TC PHN NG

I. P DNG CC QUY LUT CA THUYT VA CHM HOT NG V PHC

HOT NG CHO PHN NG TRONG DUNG DCH.

II. S SOLVAT HA.

1. Lc gia cc phn t

2. Cu trc cht lng

3. S Solvat ha phn t trung ha v ion

4. Mu Solvat ha tnh in.

III. PHN NG CA PHN T TRUNG HA DIN RA QUA TRNG THI

CHUYN TIP KHNG PHN CC.

IV. NH HNG CA PHN CC LN TC PHN NG PHN CC.

1. Phn ng ca phn t trung ho din ra qua trng thi chuyn tip cho phn cc

2. Phn ng gia cc ion

3. Phn ng gia ion v phn t trung ha.

V. NH HNG CA SOLVAT HA RING LN TC PHN NG

1. nh hng ca Solvat ha ion ln tc phn ng phn cc

2. S in ly ca ion, Solval ha cc cation v tc phn ng

CHNG VII

NH HNG CA DUNG MI LN TC PHN NG

Tuyt i a s phn ng l phn ng ca hp cht hu c din ra trong dung dch. Do vy, nghin
cu nh hng ca dung mi ln tc phn ng c ngha l thuyt cng nh thc tin quan trng.

pha lng phn t cht phn ng v dung mi tip xc vi nhau mt cch khng kht, lc tng tc
tng h gia chng tng i ln. Bn cht ca cc lc ny rt khc nhau v bao gm: lc phn tn
(khuch tn) London, l lc tng tc gia cc m my electron ca cc phn t ring r qua tng
tc tnh in; lc Culong ca cc phn t phn cc, hoc b phn cc to ra lin kt hydro v cc lin kt
ha hc ring r khc. Cho n nay, cha c kh nng m t mt cch y cc tng tc ny. V vy,
chng ta ch c mu (m hnh) v s ph thuc bn thc nghim t c s cho vic gii ng hc cc
phn ng din ra trong dung dch.

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Ni dung c bn v nh hng ca dung mi ln tc phn ng gm my vn sau:

I. p dng cc quy lut ca thuyt va chm hot ng v phc hot ng cho phn ng trong
dung dch.

II. S solvat ha.

III. Phn ng ca phn t trung ha din ra qua trng thi chuyn tip khng phn cc.
IV. nh hng ca phn cc ln tc phn ng phn cc.
V. nh hng ca solvat ha ring ln tc phn ng.

I. P DNG CC QUY LUT CA THUYT VA CHM HOT NG V PHC

HOT NG CHO PHN NG TRONG DUNG DCH

(Xem mc 5.3.10).

II. S SOLVAT HO

1 Lc gia cc phn t TOP

Hin tng solvat ha gy ra do tc dng ca lc Vander Vaals. Lc ny c ngun gc ca lc ha

tr, c sinh ra do tng tc gia electron v ht nhn nguyn t trong cc phn t, c m t bng
phng php c hc lng t.

a) Lc sinh ra do tng tc gia cc nguyn t mang in tch vi phn t, cng nh gia cc phn
t c in tch bt i xng (phn t lng cc). Trong s gn ng c th gii thch bn cht ca lc
bng tng tc tnh in. Lc lng cc ny (tng tc ion - lng cc, lng cc - lng cc) l mt
hm s ca in tch ion v momen lng cc ca phn t, lng cc gim khi tng s phn t.

b) Tng tc gia cc phn t khng phn cc hoc phn t phn cc b chim ot in tch vi
cc ion hoc phn t c momen lng cc. Cng c th m t lc ny bng mu tnh in. Lc ny ph
thuc vo phn cc ca phn t v in tch, momen lng cc ca cc phn t cm ng.

c) Lc khuch tn (hoc lc London) sinh ra do tng tc gia cc nguyn t v phn t b tc

ot in tch c momen lng cc bn. C th gii thch lc ny hnh thnh do kt qu ca s chuyn
ng ca cc electron trong nguyn t v phn t, v c m t nh mt hm s ca phn cc v th
ion ha phn t. Tng tc ny lit vo tng tc gia cc phn t. Lc tng tc gia cc phn t loi
ny l lc yu di tc dng ca n khng dn n s hnh thnh lin kt gia cc phn t. Ngc li, lc
tng tc gia cc ion hoc cc phn t lng cc c tr s ln. Ngoi ra, cn c lc tng tc c bit.
l lc lin kt hydr, lin kt cho nhn.

d) Lc lin kt hydro: Lc gy ra s hnh thnh lin kt hydro gia hai phn t cho, nhn. V d,
lin kt gia phn t axit cacboxyl vi hp cht c nhm OH th axit l phn t (cht) cho, cn ru l
cht nhn. Lin kt ny l lin kt yu, nng lng lin kt trong khong 4 - 8 Kcal/mol. Kh nng to ra
lin kt hydro l do tnh cht c trng ca cc dung mi d b proton ha nh: nc, ancol, amit, axit
cacboxyl v hp cht khc.

e) Tng tc cho nhn electron

Lin kt cho nhn electron xy ra gia cc phn t c c im cho, nhn electron.

Phn t cha electron , c th ion ha thp c tnh cht cho electron, v d, baz Levis, cn phn
t c orbital bn trong trng khng, c i lc ha hc cao l cht nhn electron. V d axit Levis.

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V d, lin kt trong phc cht l lin kt cho nhn.

2 Cu trc cht lng TOP

Lc tng tc gia cc phn t ca cng mt dung mi c tr s s khc nhau, ph thuc vo cu

trc ca phn t. Cu trc cht lng l do kt qu tng tc ca lc ny. l lc khuch tn, khng nh
hng, b. V d, trong trng hp do tng tc ca dung mi khng phn cc, hoc rt t phn cc, thu
c cht lng c cu trc nh nht dng bn. Cn do tng tc ca cc phn t phn cc, hoc b phn
cc mnh, b proton ha mnh nh tng tc khuch tn mnh, hoc tng tc dipol - dipol c nh
hng, th cng thu c dng bn ca cht lng.

V d nh hydrocacbon no l cht lng th nht, cht lng dng th hai nh nc, ancol. cht
lng ny tn ti lin kt cu hydro:

Nc l cht lng c bit, b in ly t, c th to ra lin kt cu hydro dng t din:

3 S solvat ha phn t trung ha v ion TOP

Khi chuyn cht tan t pha kh vo mi trng lng, cc phn t ca cht tan tng tc vi phn t
dung mi , do lm tng lc tng tc tng h gia cc phn t dung mi. Cht tan cng lm thay i
lc tng tc gia cc phn t dung mi v cu trc ca n. C hai yu t ny lm thay i hm nhit
ng tiu chun ca cc cht cho khi chuyn t pha kh vo dung dch, tc l lm thay i cc hm
nhit ng ca s solvat ha. Nu ch ch ti dung dch long l tng, trong khng c tng tc
gia cc phn t cht tan vi nhau, th s solvat ha gn lin vi vic lm gim th nng v lm tng s
nh hng ca cht tan v dung mi, iu dn n lm gim

S thay i trn gy ra s thay i bin thin entanpi t do solvat ha:

i lng th (1), biu th tng tc tng h gia cht tan vi dung mi, s dng i lng ny d
gii thch v tho lun hn.

C th xc nh c gi tr bng s ca cc i lng trn bng cc phng php khc nhau, v d,

da vo o tan.

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Cn lu , entanpi t do ca s hydrat ha l nh trong trng hp ca hp cht nhm k nc,

chng khng th to ra cu hydro khi c s tham gia ca nc v v th lm h thp dng ny ca lin kt
gia cc phn t nc. Do vy, m entropi v nhit hydrat ha c gi tr ln, c hai gi tr va ni u m,
v th nh hng ca n ln: c b tr mt phn. S tng nhanh entanpi v entropi khi ha tan
hp cht trung ha vo nc c th c gii thch nh sau: cc cht ny lm tng s in ly mt cch r
rt khi n b bao bc bi nc. S liu thc nghim cho thy tc dng ny gim xung, khi tng kch
thc phn t, tuy nhin, nguyn nhn ca tc dng ny cha c lm sng t.

Ngc li, cht in ly k nc ion b solvat ha trong mi trng nc. Mc hydrat tng khi
gim kch thc.

Anion b solvat ha trong mi trng nc mnh hn cation tng ng v kch thc.

T s liu thc nghim cn cho thy: entropi hydrat ha gim khng ang k, nhng gim nhiu i
vi ion , thm ch gim nhiu hn c trng hp cht khng in ly, do tng
tc tng h gia cc ion v phn t nc lm tng s nh hng ca chng v do lm gim mnh
entropi. iu c biu din bng s tn ti lp kh quyn solvat ha bao quanh ion n. Cc phn t
dung mi bao bc gn nht (trc tip) ion solvat ha to ra lp s cp.

T thc nghim cho thy, ion s b solvat ha rt mnh ngay c dung mi khng nc so vi phn
t trung ha. C s khc nhau r rt trong tng tc solvat ha ca dung mi proton ha (v d, nc,
metanol) v khng proton ha vi dung mi phn cc (v d, acetonitryl,dimetylformamid). Dung mi

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proton ha l cht cho trong lin kt hydro, bi v chng c th b solvat ha mnh. Anion l cht nhn
trong lin kt ny, dung mi khng proton ha s khng c kh nng to ra lin kt hydro. S khc nhau
ny cng r rt trong trng hp anion nh v b h thp, khi kch thc ca chng tng.

Hp cht hu c trung ha b solvat ha mnh hn trong dung mi hu c so vi trong nc. iu

ni chung ch xy ra i vi trng hp ca cc phn t ln (v d nitrobenzen). N c vai tr tng
t nh trong trng hp ion hu c ln.

4 Mu solvat ha tnh in TOP

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III. PHN NG CA PHN T TRUNG HO DIN RA QUA TRNG THI

CHUYN TIP KHNG PHN CC

Trong trng hp ny s solvat ha cht tham gia phn ng khng khc nhiu so vi s solvat ha
trong trng thi chuyn tip. Do , khng c nh hng ca dung mi ln tc phn ng.

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IV. NH HNG CA PHN CC LN TC PHN NG PHN CC

S khc nhau nhiu v gi tr entropi t do ca s solvat ha phn t khng phn cc trung ha,
cng nh phn t, ion phn cc. l nguyn nhn gy nh hng r rt ln tc phn ng i vi
nhng phn ng c trng thi chuyn tip v trng thi ban u khc nhau nhiu v phn cc.

1 Phn ng ca phn t trung ha din ra qua trng thi chuyn tip phn cc TOP

2 Phn ng gia cc ion TOP

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V d v loi phn ng ny:

NH4(+) + OCN(-) ( NH2CONH2 (Ur)

3 Phn ng gia ion v phn t trung ha TOP

Phn ng ca ion vi phn t trung ha din ra qua trng thi chuyn tip c in tch hiu dng
nh trng thi u, khi ch ti lc tnh in i vi h s hot ca phc hot ng, nu b qua nh
hng ca dung mi ln h s hot ca phn t trung ha, thu c:

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Nu trng thi chuyn tip c phn cc cao hn cht phn ng, th tc phn ng tng khi tng
hng s in mi trong hn hp dung mi. ng biu din khng phi lun lun l ng thng. C th
l cc dng ng cong khc nhau, i vi phn ng trong hn hp dung mi khc nhau v nhn c
lch c du khc nhau. Gy ra s sai lch trn l do c s n gin ha m hnh - coi dung mi nh h
in mi lin tc.

Mt s v d loi phn ng ny:

OH(-) + CH3 - I [OHd-... CH3... Id-]* CH3OH + I(-)

V. NH HNG CA SOLVAT HO RING LN TC PHN NG

C th gii thch nh hng ca dung mi ln hot tnh ca cht tan. Dung mi tc dng khng ch
nh l mi trng in mi lin tc to ra in tch hay t hp phn t, m cn tham gia vo tng tc
gia cc phn t ring r - gia cc phn t dung mi v phn t cht tan lm cho phn t cht tan n
nh mc nht nh. l tng tc ring r ch yu sau:

a) Solvat ha cation (hoc in tch m) qua lin kt hydro c hnh thnh nh s c mt ca dung
mi proton ha nh nc, ancol, phenol, axit cacboxyl amin axit (nhm OH, NH).

b) Solvat ha cation (hnh thnh phc cho - nhn) vi dung mi m phn t ca n c nguyn t
cha cp electron t do, v d nh oxy, nit. iu xy ra khng ch i vi dung mi khng proton ha
nh ete, aceton, axit disunfonic, dimetyl fomamid v c dung mi proton ha.

c) Solvat ha phn t trung ha to ra cu trc cu hydro (tng tc cho - nhn).

1 nh hng ca s solvat ha anion ln tc phn ng phn cc TOP

Kh nng ca dung mi i vi s solvat ha anion in tch m qua cu hydro thng quyt nh
nh hng ca n ln tc phn ng phn cc. Nh solvat ha anion tr nn n nh, ha th ca n

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gim, do hot tnh b gim.

Trong dung mi phn cc khng proton ha khng th hnh thnh lin kt hydro, anion b solvat
ha mc khng nhiu. Ngc li, trong dung mi proton ha, anion nh b, b solvat ha mnh qua
lin kt hydro.

2 S in ly ca ion, solvat ha cation v tc phn ng TOP

Siemioczenko, Bjerrum cho rng, cht in gii mnh khng nht thit in ly mt cch hon ton
tr thnh ion t do b solvat ha, m cn ion c int ch ngc du c th b in ly gy ra do lc ht
tnh in to ra ion kp, ba, lc thit lp cn bng gia cp ion in ly:

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Bi tp chng VII

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3. Cho bit nguyn nhn gy ra s thay i tc phn ng trong dung dch.

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