8/30/2015

NI DUNG
THUYT ACID BASE ARRHENIUS

CHNG 2

THUYT ACID BASE BRONSTED-LOWRY

CC THUYT ACID &

BASE

THUYT ACID BASE LEWIS

THUYT ACID BASE USANOVICH & LUX-FLOOD

1. THUYT ACID BASE ARRHENIUS

2. THUYT ACID BASE BRONSTED-LOWRY

nh ngha: Acid l cht phn ly trong nc cho

ion H+, base l cht phn ly trong nc cho ion OH

tiu phn nhn proton trong phn ng.

V d:

HCl (k)

H O
2

nh ngha: Acid l tiu phn cho proton (H+), base

V d:

HCl H+ + Cl-

H+(aq) + Cl-(aq)

H2SO4 H+ + HSO4NaOH (r)

H O
2

Na+(aq)

OH-(aq)

2 v d trn, cc cp acid, base HCl/Cl- v

H2SO4/HSO4-, gi l cp acid/base lin hp

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2. THUYT ACID BASE BRONSTED-LOWRY

ACID
TRUNG
HO

BASE

HCl H+ + Cl-

ANION

HSO4

H+

H2O + H+ H3O+
2-

+ SO4

HCO3- H+ + CO32CATION

Lu : Do H+ khng tn ti dng t do, nn

cc acid ch cho proton khi c base nhn, v
ngc li.

Phn ng trao i proton (tng qut) xy ra gia

hai cp acid/base lin hp nh sau:

NH3 + H+ NH4+

H2O H+ + OH-

2. THUYT ACID BASE BRONSTED-LOWRY

CH3COO- +H+CH3COOH
Cl- + H+ HCl

A1 + B2 A2 + B1

NH4+ H+ + NH3
H3O+ H+ + H2O

2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

Cng acid-base Bronsted trng thi kh

Trong dung dch, cc phn t hoc ion do dung mi

in ly ra cng ng vai tr ca cp acid-base lin
hp: H3O+/H2O; H2O/OH-

C th nh gi kh nng nhn H+ ca mt base thng qua

nhiu ng nhit ca qu trnh trong pha kh

Nhn xt: cc hp cht cha H+ lun l cht lng

tnh, n ph thuc vo cht phn ng vi n c kh
nng cho/nhn H+ mnh hay yu hn n.

B (k) + H+(k) = BH+(k), H = -Q

Q l nng lng gii phng ra ca qu trnh.
Q cng ln th H cng m, qu trnh kt hp cng mnh
Base B cng mnh th acid lin hp BH+ cng yu

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2. THUYT ACID BASE BRONSTED-LOWRY

BNG CC GI TR Q (kJ/mol)
Ion

Phan t

Ion

1674

H2

423

F-

1554

F2

399

PH2-

1541

PH3

789

Cl-

1398

HCl

564

AsH2-

1501

AsH3

Br-

1354

HBr

589

552

I-

1315

HI

628

H 2O

679

H2S

712

H2 Se

717

CH3-

1743

N3-

3084

CH4

O2-

2318

NH2-

2565

OH-

1635

NH2-

1689

NH3

85

S2-

2300

NCl3

795

SH-

1478

NF3

556

Se2-

2200

SeH-

1420

xc nh cng ca cc acid, c th da trn

cc gi tr Q ca cc base lin hp ca n

Phan t

H-

2. THUYT ACID BASE BRONSTED-LOWRY

V d:
F-(k) + HCl(k) = HF(k) + Cl-(k)
Q (kJ/mol) 1554

1398

F- l base mnh hn Cl- (Q ca F- ln hn), nn Fly c H+ ca HCl.

Lu : Q cng ln, tnh acid cng yu.
9

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2. THUYT ACID BASE BRONSTED-LOWRY

Dung mi proton ha: dung mi c th t ion ha
mt phn khi trng tho lng to ra H+.

2. THUYT ACID BASE BRONSTED-LOWRY

Dung mi proton ha:

Do H+ khng c lp v electron, l in tch im vi

in tch dng rt cao. Nn khi trng thi lng, H+
khng tn ti dng t do m lun b solvat ha bi
cc tiu phn bao xung quanh n.

Tng qut, vi dung mi proton ha HSol :

HSol + HSol H2Sol+ + Sol- , KS

Hng s t proton ha (KS):

KS= [H2Sol+][Sol- ]

Cc dung mi proton ha l: H2O(l), NH3(l),

H2SO4(l), HCl(l)

i vi nc, KS= [H3O+][OH- ] = 10-14 220C.

Vi nc: H2O + H2O = H3O+ + OH11

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2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

Dung mi proton ha: l nhng cht lng tnh

(theo acid-base Bronsted).

Dung mi proton ha:

Cng acid-base cng c xt trn i lc proton ca
chng, Hs = -Qs

Trong cc dung mi proton ha c mt 2 cp

acid/base lin hp:

Lu : Qs Q trng thi kh.

V d: trng thi kh:

Sol- + H+ HSol (HSol/Sol-)

H+(k) + OH-(k) = H2O(k), H= - Q= -1635kJ/mol

HSol + H+ H2Sol+ (H2Sol+/HSol)

trng thi lng:

H+(aq) + OH-(aq) = H2O(l), H= - Qs = -1188kJ/mol

H+(aq) + H2O(l) = H3O+(aq), H= -Qs = -1130kJ/mol

Lu : Khi ha tan 1 cht, Qs phu thuc vo dung mi, Qs ln

th tnh base mnh.

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2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

Vi acid HA trong H2O:

HA + H2O H3O+ + ANu HA mnh hn H3O+ th cn bng dch chuyn theo chiu
thun Trong nc khng c acid mnh hn H3O+.
Vi base B trong H2O:
B + H2O BH + OHNu B l base mnh hn th cn bng dch chuyn theo chiu
thun Trong nc khng c base mnh hn OH-.
mnh ca acid/base ph thuc vo mnh ca dung mi,
c nh gi bng hng s cn bng trong qu trnh trao i
proton ca cht vi dung mi.
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Cng ca acid HA ha tan trong dung mi

proton ha c nh gi bi hng s cn bng
sau: HA + HSol H2Sol+ + A-

[ H 2 Sol ][ A ]
[ H Sol ][ A ]
K [ HSol] K a 2
[ HA][ HSol]
[ HA]

Trong H2O:

Trong : Ka l hng s acid

Ka

[ H 3O ][ A ]
[ HA]

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2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

Ka cng ln th tnh acid cng mnh.

Ka ph thuc vo bn cht ca acid, nhit v dung

mi.

Nu dung mi th hin tnh base cng mnh th HA

th hin tnh acid cng mnh.

VD: HClO4 l acid rt mnh trong dung dch nc

(Ka=1010), nhng trong CH3COOH, HClO4 li l
acid yu (Ka=10-6)

Tng t:
B + HSol HB+ + Sol-

Kb

[ HB ][ Sol ]
[ B]

Kb cng ln th tnh base cng mnh.

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MT S ACID BASE LIN HP

2. THUYT ACID BASE BRONSTED-LOWRY

Lin h gia Ka v Kb:

Ka

HI

3 x 109

HCl

Trong mt cp acid/base lin hp:

H2SO4

HA + HSol H2Sol+ + A-

H3

A- + HSol HA + SolVi

Ka

[ H 3O ][ A ]
[ HA]

Kb

[ HB ][ Sol ]
[ B]

Ka Kb = [HSol+][Sol-] = Ks

Acid

Trong dung dch nc: KaKb = Kn = 10-14 220C.

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O+

1x

106

1x

103

pKa

Base lien hp

Kb

-9.5

I-

3 x 10-24

-6

Cl-

-3

HSO4

pKb
23.5

1x

10-20

20

1x

10-17

17

10-16

15.7

55

-1.7

H2 O

1.8 x

HNO3

28

-1.4

NO3-

3.6 x 10-16

15.4

H3PO4

7.1 x 10-3

2.1

H2PO4-

1.4 x 10-12

11.9

CH3CO2H

1.8 x 10-5

4.7

CH3CO2-

5.6 x 10-10

9.3

H2 S

1.0 x 10-7

7.0

HS-

1 x 10-7

7.0

H2 O

1.8 x 10-16

15.7

OH-

55

-1.7

CH3OH

1 x 10-18

18

CH3O-

1 x 104

-4

HCCH

1 x 10-25

25

HCC-

1 x 1011

-11

NH3

1 x 10-33

33

NH2-

1 x 1019

-19

H2

1 x 10-35

35

H-

1 x 1021

-21

CH2=CH2

1 x 10-44

44

CH2=CH-

1 x 1030

-30

CH4

1 x 10-49

49

CH3-

1 x 1035

-35

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2. THUYT ACID BASE BRONSTED-LOWRY

Trong mt chu k, t tri sang phi, i lc electron tng

dn, nn tnh acid tng.

2. THUYT ACID BASE BRONSTED-LOWRY

Cc acid cha Oxy, H hoc nhm OH th tnh acid ph thuc

vo m in ca nguyn t trung tm lm phn cc ca
lin kt O-H hay X-H thay i dn n thay i cng acid.

Cc hydroxyt lng tnh: nguyn t trung tm l kim loi km

hot ng hay phi kim c m in nh (hai lin kt M-OH
v O-H c phn cc gn nhau) Tnh acid/base ph
thuc vo mi trng (dung mi):

VD: Tnh acid HF > H2O

Trong mt phn nhn, khi i t trn xung, bn lin

kt gairm nhanh hn i lc electron, nn tnh acid tng.
VD: Tnh acid HF < HCl < HBr

OH- + M MOH MO- + H+

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2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

Quy lut bin i cng ca acid-oxy

Quy lut bin i cng ca acid-oxy

(Quy tc Pauling)

(Quy tc Pauling)

Acid-oxy: HaXOn(OH)m (X: nguyn t trung tm).

a: S nguyn t H lin kt trc tip vi X.
n: S nguyn t O lin kt vi X nhng khnglin kt vi
H.
m: S nhm OH lin kt vi X.
n quyt nh cng acid.

n=0 acid rt yu.

VD: Te(OH)6, Cl(OH)

n=1 acid yu.

n=2 acid mnh.

VD: NO(OH), PO(OH)3, SO(OH)2

VD: SO2(OH)2, ClO2(OH), NO2(OH)

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n=3 acid rat manh.

VD: ClO3(OH)

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2. THUYT ACID BASE BRONSTED-LOWRY

Nhn xt:
OH, H lin kt vi X khng nh hng nhiu n cng
acid (do O lin kt trc tip X ht e mnh X cng
dng, nn lin kt O-H cng b phn cc d H+).
Cc cng thc c cng cu trc (a,m,n), nu X tng m
in s lm tnh acid tng (nhng khng r rt).
Tnh Ka (Quy tc thc nghim Pauling): acid
HaXOn(OH)m. pKa = 7-5n
Quy tc ny tnh pKa1 gn ng khi bit cu trc.
VD:
o HClO (n=0) c pKa = 7.
o H2SO4 (n=2) c pKa = -3.
Vi cc bc tip theo: pKa(n+1) = pKa(n) + 5

2. THUYT ACID BASE BRONSTED-LOWRY

PHN NG THY PHN THEO BRONSTED-LOWRY

Thy phn trong dung dch nc: V bn cht l cc phn

ng trao i proton gia cc ion do mui phn ly vo cc phn
t nc.

Thy phn cation: Xy ra khi khi cation l cc acid mnh hn

nc, n nhng H+ cho nc (M+ djang dung dch).

[M(H2O)m]+n + H2O [M(H2O)m-1OH]+(n-1)+H3O+

Hng s thy phn Ktp ca acid [M(H2O)m]+n ?

Mc thy phn s tng dn theo mnh ca acid, tc l

cation c Ktp nh hn th tnh acid mnh hn d thy phn
hn.

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2. THUYT ACID BASE BRONSTED-LOWRY

2. THUYT ACID BASE BRONSTED-LOWRY

PHN NG THY PHN THEO BRONSTED-LOWRY

PHN NG THY PHN THEO BRONSTED-LOWRY

S thy phn ca cation ph thuc vo in tch (s OXH), bn

knh ion v cu hnh electron.

VD: Mn2+ (pKtp = 10.7) v Hg2+ (pKtp = 3.7) th Hg2+ c tnh

acid mnh hn v thy phn mnh hn.

Anion ca mui l base, nu mnh hn nc th n s ly H+

ca nc OH- tng.

A- + H2O AH + OH mnh ca base da vo acid lin hp ca n

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Cc anion l base qu mnh (O2-, N3-) b thy phn hon ton

khng tm ti ion ny trong dung dch.
O2- + H2O 2OH-

Cc base yu hn nc khng b thy phn.

VD: SO42- (Kb=10-11) hu nh b thy phn
Mi gm cation v anion: nu ch c cation b thy phn
mi trng acid, nu ch c anion b thy phn mi trng
base. Nu c hai b thy phn th pH dung dch do iion b thy
phn mnh hn quyt nh.

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2. THUYT ACID BASE BRONSTED-LOWRY

THY PHN CC HP CHT CNG HA TR

Cc hp cht cng ha tr khng b thy phn trong nc m

khng chu s phn hy khng thun nghch ca nc, phn
ng thy to thnh 2 acid: acid oxy-oxy v hydraxit (hydroacid).
VD: BCl3 + 3H2O H3BO3 + 3HCl
SiCl4 + 4H2O H4SiO4 + 4HCl

3. THUYT ACID BASE LEWIS

Base Lewis: l cht cho cp electron v acid l cht nhn cp

electron to lin kt ha hc. (lin kt cho nhn?).

Acid Lewis: L nhng tiu phn d mt in tch dng,

trong phn t (ion) c cc orbital trng c th nhn cc cp
electron chuyn n t cc base.

VD: a s cation (Ag+, Co3+, Cr3+), hay cc halogenua ca

B, Al, Si, Sn, P , cc hydrua ca B, Al u l acid Lewis.

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3. THUYT ACID BASE LEWIS

3. THUYT ACID BASE LEWIS

Base Lewis: L nhng tiu phn c kh nng cho i cp

electron.
VD: cc anion (Cl-, Br-, OH-) cc phn t trung ha hoc ion
trong thnh phn c cc nguyn t cn cp electron cha lin
kt nh N, O (NH3, ru, cetone).
Ag+ + NH3 [Ag(NH3)2]+
BF3 +

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Cng acid-base Lewis

Rt kh so snh cng acid-base Lewis v cn ph thuc
vo lin kt cng ha tr gia cc cht.
C th xc nh da trn: s phn ly trong pha kh, so snh
bn ca sn phm to thnh gia cc acid v base.
V d tnh base ca dy sau gim dn:

F- [BF4]-

H phn ng vi
B(methyl)3(kJ/mol)

Hp cht

HCl + NH3 NH4Cl

31

(Methyl)3N

-74

(Methyl)3P

-67

(Methyl)3As

Phn ng di

(Methyl)3Pb

Khng phn ng

Tnh cht sn phm phn

ng vi HCl
Thng hoa 2500C
Thng hoa 1250C

-800C

Khng bn (to thng)

Khng bn trn -800C

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3. THUYT ACID BASE LEWIS

3. THUYT ACID BASE LEWIS

Cng acid-base Lewis

Cng acid-base Lewis

Cc hiu ng cm ng, cng hng, khng gian, c tc dng rt

electron lm tnh acid tng v tnh base gim.
i vi phc cht, khi ch xt lin kt gia nguyn t trung tm
nhn cp e ( acid) v phi t cho cp e (base), th tnh tnh acid
tng t l vi mt in tch dng trn nguyn t trung tm
v tnh base tng t l vi mt e trn phi t.

Hiu ng cm ng:
V d:
Tnh base trong dy sau gam dn: Li3N, NH3 , NF3 do tc dng
rt e ca cc Li, H, F tng dn.

VD: Tnh base trong dy sau tng:

I-<Br-<Cl-<F- , do ra -

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3. THUYT ACID BASE LEWIS

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3. THUYT ACID BASE LEWIS

Cng acid-base Lewis

Cng acid-base Lewis

Hiu ng khng gian:

Hiu ng cng hng:

V d: mc d nhm metyl c hiu ng cm ng y electron

nhng tnh base trong dy 3-metylpyridin (CH3C5H5N)(b),
pyridin (C5H5N)(a), 2-metylpyridin (c) trong phn ng vi
B(CH3)3 (trimetylbor) gam l do s cn tr khng gian ca
nhm metyl ti N. Ho298 ca cc phn ng trn ln lt l: 71kJ, -74kJ, -42kJ

V d:

Ngoi ra, hiu ng khng gian cn ohuj thuc kh nng to lin

kt ca acid v base ( phn phc cht).
35

Tnh acid trong dy BF3, BCl3, BBr3 tng dn do hiu ng

chuyn e t Halogen sang Bor to lin kt theo c ch cho
nhn. Hiu ng ny yu dn t F n Br, lm cho mt in
tch dng trn B tng dn t BF3 n BBr3.
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3. THUYT ACID BASE LEWIS

3. THUYT ACID BASE LEWIS

Phn ng to phc

Kt lun

( ging trong phn phc cht)

Ch c th tnh c mnh acid-base Lewis cho tng

nhm cht, khng c thc o chung nh trng hp acidbase Bronsted-Lawry.
mnh acid-base Lewis tnh theo nng lng lin kt
(j/mol) to thnh t acid v base Lewis hoc theo hng s
bn ca phc trong dung dch.

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3. THUYT ACID BASE LEWIS

Acid-base cng, mm
Acid cng: cation hoc phn t c kch thc nh, mt in
tch dng cao, khng c kh nng cho e, kh b bin dng. Acid
mm c kch thc ln, d b phn cc, d nhn e.
Acid cng: H+, Ca2+, Al3+
Acid mm: Cu+, Ag+, GaCl3
Base cng: Anion hoc phn t c kch thc nh, kh b bin
dng, khng c kh nng nhn e. Base mm c kch thc ln,
d b phn cc, d nhn e.
Base cng: F-, Cl-, OH-, NH3
Base mm: I-, CN-, C2H4
Tm li: cc acid hay base cng kh cho hay nhn e v cng kh
b bin dng th cng cng. C acid base khng cng khng
39
mm.

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3. THUYT ACID BASE LEWIS

Acid-base cng, mm
Quy tc phn ng:
Cc acid cng d phn ng vi base cng to cc hp cht bn,
tng t cho acid/base mm.
Chn 1 acid hoc 1 base lm chun, xc nh bn ca cc hp
cht to thnh ca n v cc acid/base khc so snh cng.
Base trong dy sau c cng tng dn:
Te2+<Se2+<S2-<I-<Br-<O2-<Cl-<OH-<CO32-<NO3-<SO42-<F- (cng
nht)
Acid trong dy sau c cng tng dn:
Ag+<Hg+<Cu2+<Cd2+<Cu+<Fe2+<Co2+<Ni2+<Fe3+<Co3+<Bi3+<
Cr3+<Mg2+<Ti4+<Nb5+<Zn4+<Al3+<Be2+
40

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3. THUYT ACID BASE LEWIS

Acid-Base cng
Al3+

F-

pK1

pK12

pK123

-7,10

-11,98

-15,83

pK1234

pK12345

pK123456
-20,67

-18,53

-20,20

Acid-Base mm

pK1

pK12

Cu+

Cl-

-5,35

-5,63

Br-

-5,92

I-

3. THUYT ACID BASE LEWIS

mnh Acid-base
nh gi kh nng t xy ra ca phn ng acid base
bng mnh acid base ca cht:
Nguyn tc: Tnh acid-base ca cc cht tham gia phn
ng cng khc xa nhau, phn ng cng d xy ra hon
ton.
mnh ca acid ph thuc vo:

-8,85

Bn cht ca nguyn t to acid hay base.

S oxy ha ca nguyn t to acid hay base.
Trng thi cu to ca cht
Mi trng xy ra phn ng

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3. THUYT ACID BASE LEWIS

3. THUYT ACID BASE LEWIS

mnh Acid-base
nh gi theo bn cht nguyn t:

mnh Acid-base
nh gi theo mc oxy ha ca nguyn t:
V d: So snh tnh acid v tnh base ca dy sau:
MnO Mn2O3 MnO2 Mn2O5 MnO3 Mn2O7

Nguyn t c tnh kim loi cng mnh th hp cht cng c tnh

base, nguyn t c tnh phi kim cng mnh th hp cht ca n
cng c tnh acid.

nh gi theo mc oxy ha ca nguyn t:

i vi hp cht cng mt loi nguyn t, mc oxy ha ca
nguyn t cng tng th tnh acid ca hp cht tng.

MnO: Oxit base, d tan trong acid long.

Mn2O3 v MnO2: Oxit lng tnh, tnh acid v tnh

base u rt yu.

MnO(r) + 2HCl(dd) = MnCl2(dd) + H2O

MnO2(r) + c,nng) = MnCl4(dd) + H2O

ion Mn4+ l chast OXH rt mnh nn MnCl4 tip tc phn ng t
oxy ha kh
MnCl4(dd) = MnCl2 + Cl2(k)
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3. THUYT ACID BASE LEWIS

3. THUYT ACID BASE LEWIS

mnh Acid-base
nh gi theo mc oxy ha ca nguyn t:

mnh Acid-base
nh gi theo kh nng phn ng vi dung mi:

Mn2O7: l anhidrit ca acid mnh (HMnO4; pK = 2,3).

Xt mnh ca Ca(OH)2 trong dung dch nc:

Ca l kim loi mnh, m in bng 1.0, (o) = -2,76V d
on Ca(OH)2 l mt base mnh in ly hon ton trong nc.

D dng phn ng vi nc hay vi dung dch base long

Mn2O7(r) + H2O(lnh) = 2HMnO4 (dd)
Mn2O7(r) + 2NaOH(dd) = 2NaMnO4(dd) + H2O

Tuy nhin thc t Ca(OH)2 l mt base c mnh trung bnh.

(Dung dnh bo ha canxi hydroxit 30oC c pH 0,9)

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4. THUYT ACID-BASE USANOVICH V

LUX-FLOOD

3. THUYT ACID BASE LEWIS

mnh Acid-base
nh gi theo mi trng phn ng:
So snh mc thy phn ca mui nhm sulfat:

T (Al(OH)3) = 1.10-32, Kkb([AlF6]3-) = 1.10-20,67, KHF = 1.10-3,18

Khi khng c ion

F-:

Al3+.aq + 3H2O = Al(OH)3 + 3H+.aq

Kcb* = K3H2O/TAl(OH)3 = 1.10-6

Khi c ion F-:

[AlF6]3-.aq + 3H2O = Al(OH)3 + 3HF+ 6FKcb** = Kkb. K3H2O/TAl(OH)3.K3HF = 1. 10-17,13

Thuyt Usanovich
Acid l nhng cht c th cho i cation, kt hp anion
hoc e.
Base l nhng cht c th cho i anion, kt hp vi
cation.
Mi tng tc u c th xem l phn ng acid-base,
k c phn ng c s trao i e (p/ O-Kh).
VD: Acid
+ Base
BF3
+ KF K+ + BF4-.
AlF4
+ NaF Na+ + [AlF6]-3.

Khi khng c ion F-, ion Al3+ thy phn gp:

Kcb*/Kc** = 1.10-6/1.10-17,13 = 1011,13 ln

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4. THUYT ACID-BASE USANOVICH V

LUX-FLOOD

4. THUYT ACID-BASE USANOVICH V

LUX-FLOOD

Thuyt Lux

Thuyt Lux
Phn ng kt hp: c xp vo phn ng acid-base
VD: CaO(r) + SiO2(r) = CaSiO3 (r)
base
acid
NaOH(r) + CO2(k) NaHCO3(r)
base
acid

Acid l nhng cht c kh nng nhn anion O2Base l nhng cht c th cho i anionO2-.
VD: Acid
Base
SiO2 + CaO CaSiO3
CO2 + MgO MgCO3
S2O72-+ NO3- NO2+ + 2SO42-

Thuyt Lux-Flood v Usanovich cho php gii thch phn ng ca

cc cht trng thi nng chy.
VD: 3ZnO + P2O5 3Zn2+ + 2PO43K2O + ZnO K+ + ZnO2Lu : cc thuyt acid-base khng mu thun nhau m ch khc
nhau phm vi ng dng.
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