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MC LC

MC LC................................................................................................................. 1
Phn M U.........................................................................................................3
Phn 1 C S L THUYT.....................................................................................4
1.1.Khi nim axit-baz............................................................................................4
1.1.1. Thuyt axit-baz ca Bronsted v Lowry.......................................................4
1.1.2. Thuyt axit-baz ca Lewis............................................................................4
1.1.3. Thang pH v pOH...........................................................................................5
1.2.Vn chung v cht in li trong dung dch.....................................................5
1.2.1. Cht in li v s in li..................................................................................5
1.2.2. in li v hng s in li...........................................................................6
1.2.2.1. in li......................................................................................................6
1.2.2.2 Hng s in li..............................................................................................6
1.2.3. Phn loi cht in li.......................................................................................7
1.2.3.1 Cht in li mnh v cht in li yu............................................................7
1.2.3.2 Biu din trng thi cht in li trong dung dch..........................................7
1.3.Nhng nh lut c bn tnh ton cn bng trong dung dch axit baz.......8
1.3.1.nh lut bo ton vt cht.............................................................................8
1.3.1.1nh lut bo ton nng ...........................................................................8
1.3.1.2.nh lut bo ton in tch.......................................................................10
1.3.2. nh lut tc dng khi lng.....................................................................10
1.3.3.nh lut bo ton proton (iu kin proton)...............................................12
1.4.Cn bng trong dung dch axit baz...............................................................13
1.4.1.Dung dch cc n axit baz.......................................................................13
1.4.1.1.n axit mnh............................................................................................13
1.4.1.2.n baz mnh..........................................................................................13
1.4.1.3.n axit yu...............................................................................................15
1.4.1.4.n baz yu.............................................................................................16
1.4.2.Dung dch ca cc hn hp axit baz .......................................................18
1.4.2.1.Hn hp axit mnh v axit yu...................................................................18
1.4.2.2.Hn hp baz mnh v baz yu................................................................19
1.4.2.3.Hn hp n axit.........................................................................................20
1.4.2.4.Hn hp n baz.......................................................................................21
[1]

1.4.2.5.Hn hp n axit yu v baz lin hp......................................................22


1.4.3.Dung dch cc a axit baz.........................................................................24
1.4.3.1.a axit........................................................................................................24
1.4.3.2.a baz......................................................................................................25
Phn 2 PHNG PHP TH LOGARIT GII BI TON pH...................26
2.1.Tnh ton cn bng trong cc dung dch axit....................................................26
2.1.1.Dung dch n axit mnh...............................................................................26
2.1.2.Dung dch n axit yu ..................................................................................27
2.1.3.Hn hp axit mnh v axit yu......................................................................29
2.1.4.Hn hp n axit ...........................................................................................30
2.1.5.a axit ...........................................................................................................32
2.2.Tnh ton cn bng trong cc dung dch baz ..................................................35
2.2. 1. Dung dch n baz mnh............................................................................35
2.2.2.Dung dch n baz yu.................................................................................36
2.2.3. Hn hp baz mnh v baz yu..................................................................38
2.2.4. Hn hp n baz.........................................................................................39
2.2.5 .a baz.........................................................................................................41
2.3. Hn hp n axit yu v baz lin hp...........................................................43
Phn 3 KT LUN.................................................................................................46
TI LIU THAM KHO.......................................................................................47

Phn M U
Trong 10 ho cht m th gii sn xut nhiu nht hin nay c n 6 cht l axit
[2]

hoc baz, l: H2SO4, CaO, NH3, NaOH, H3PO4 v HNO3. Phn ng axit baz
l phn ng rt quan trng c v mt nghin cu l thuyt v mt ng dng ha hc
vo thc tin.
Phn ln cc phn ng ha hc u c din ra trong dung dch nc, i vi
dung dch nc do trong thnh phn dung dch lun c s hin din ca ion H+ v
OH-. S c mt thng xuyn ca hai ion ny trong thnh phn dung dch gy ra
nhng nh hng trc tip hoc gin tip n cc cn bng khc trong dung dch.
Tnh axit hay baz ca dung dch c nh hng rt ln n cc qu trnh xy ra
trong dung dch nh kh nng to phc ca ion kim loi, phn ng oxi ha kh, kh
nng b thu phn ca cc ion kim loi
Do , vic tnh ton cn bng trong dung dch axit baz gi vai tr quan trng
khng ch i vi ha phn tch m c vi ha hc ni chung. Tuy nhin vic tnh ton
cn bng trong dung dch axit baz l kh phc tp v trong dung dch c nhiu cn
bng xy ra chn cn bng no ch yu l rt kh khn.
Trn nhng c s nhm 13 quyt nh chn ti Cn bng axit baz trong
dung dch phng php th logarit gii bi ton pH.
Trong phm vi nghin cu ca ti ny, nhim v t ra l:
- Nghin cu thut ton, lp chng trnh tnh v v chnh xc gin logarit
nng ca cc ion trong dung dch axit baz.
- Da vo gin v phng trnh iu kin proton tnh ton cn bng xy ra
trong dung dch axit baz (loi b phng trnh cn bng ph khng nh hng
nhiu n tnh axit baz ca dung dch).

Phn 1 C S L THUYT
1.1. Khi nim axit-baz:
[3]

1.1.1. Thuyt axit-baz ca Bronsted v Lowry:


Ngi u tin a ra cc nh ngha v axit v baz gn gi vi quan im hin
i l Svate Arrhnius (1859 - 1927). Da trn cc kho st thc nghim v cht
in li, ng cho rng:
- Axit l cht c kh nng phn li cho H+ khi ha tan vo nc.
- Baz l cht c kh nng phn li cho OH- khi ha tan vo nc.
Vo thi im , y l mt bc tin quan trng trong vic nh lng axit
baz. Nhng thuyt ny b gii hn ch ch gii thch c tnh axit-baz ca cc
hidro axit v cc hidroxit; khng ni ln c vai tr ca dung mi.
Mt nh ngha tng qut hn c ngh bi nh ha hc an Mch:
Jonhannes K.Bronsted v nh ha hc ngi Anh: Thomas Lowry. Theo thuyt ny:
- Axit l cht c kh nng cho proton H+
- Baz l cht c kh nng nhn proton H+
Thuyt axit baz ca Bronsted v Lowry bao hm thuyt axit-baz ca
Arrhenius, v m rng ra cho cc dung mi khc nc cng nh cho cc phn ng xy
ra trng thi kh.
V d 1.1:
NH3 + HCl NH4Cl
Trong phn ng ny NH3 l cht nhn H+, HCl l cht cho H+ v do NH3
l baz, HCl l axit.
1.1.2. Thuyt axit-baz ca Lewis:
Mt thuyt tng qut hn na v axit baz c G.N.Lewis a ra. Theo thuyt
Lewis:
- Axit l cht c kh nng nhn thm mt hay nhiu cp electron ca cht khc
hnh thnh lin kt cng ha tr mi.
- Baz l cht c kh nng nhng mt hay nhiu cp electron cha lin kt cho
cht khc to thnh lin kt cng ha tr mi.
Do , mt axit Lewis phi c t nht mt obitan ha tr trng nhn cp electron,
cn mt baz Lewis phi c t nht mt i electron cha lin kt . T y ta thy nh
ngha axit baz ca Lewis bao hm nh ngha ca Bronsted v Lowry.
V d 1.2: H+ + NH3 [H3N :H]+
Trong phn ng ny NH3 l mt baz v l cht cho i electron, H+ l axit v l
cht nhn mt i elcetron.
Gi tr ca thuyt Lewis v axit-baz l ch gii thch c cc phn ng axit
baz theo quan im ca Bronsted v Lowry, hn th na cn gii thch c mt s
phn ng axit baz m thuyt Bronsted v Lowry khng gii thch c.
V d 1.3: Phn ng gia Trifluorua bor v amoniac:
[4]

BF3 + NH3

F3B-NH3

BF3 l phn t thiu electron, xung quanh nguyn t Bo ch mi c 6 electron,


khi phn ng vi NH3, nguyn t Bo s t c c cu 8 electron. BF3 l mt cht c
i lc mnh vi cc cht cho electron v do l mt axit Lewis mnh.
Thuyt axit-baz ca Lewis cng gii thch thnh cng qu trnh hydrat ha ca
ion kim loi.
V d 1.4:
Al3+ + 6H2O Al(H2O)63+
Al3+ l cht nhn electron t nguyn t oxi ca nc l axit v nc l baz.
Rng ra hn na phn ng gia mt oxit axit v nc, theo thuyt Lewis cng l
mt phn ng axit baz, trong oxit axit l cht nhn mt i electron nn l
axit, nc l cht cho mt i electron nn l baz.
1.1.3. Thang pH v pOH:
Do nng H+ trong dung dch nc thng l nh, nn ngi ta a ra nh
ngha pH v pOH nh gi tnh axit baz ca mt dung dch cho tin li. pH v
pOH ca mt dung dch c nh ngha nh sau:
pH = -lg[H+] v pOH = -lg[OH-]
V: [H+][OH ] = 10-14 pH + pOH = 14
- i vi dung dch trung tnh [H+] = [OH-] nn pH = pOH = 7
- i vi dung dch axit [H+] > [OH-] nn pH < pOH
- i vi dung dch baz [H+] < [OH-] nn pH > pOH
Tng t nh th, ngi ta nh ngha pK = - lgK. Vi K l hng s phn li ca
cc cht.
Gi tr pH ca mt dung dch c th c xc nh bng my o pH hay giy o
pH.
1.2. Vn chung v cht in li trong dung dch:
1.2.1. Cht in li v s in li.
Khi ha tan cc cht c lin kt ion hoc lin kt cng ha tr c cc vo trong
dung mi phn cc (v d: nc, ru) th do s tng tc vi cc phn t lng
cc ca dung mi m cc phn t cht tan s phn li hon ton hoc mt phn thnh
cc ion mang in tch tri du, tn ti dng ion sonvat ha (i vi dung mi nc l
ion hirat ha). Cc cht c kh nng phn li thnh cc ion c gi l cht in li, v
qu trnh phn li gi l qu trnh in li.
V d 2.1: khi ha tan cht in li MX vo nc
Thng thng ta
khng bit chnh xc s phn t nc x, y trong cc ion hirat ha nn ngi ta biu
[5]

din s phn li theo s n gin:


MX Mn+ + Xn- (2.1)
Vi ngm hiu l Mn+, Xn- ch cc ion hirat ha. Mc phn li thnh ion
ca cc cht in li ph thuc vo bn cht ca cc cht in li v bn cht ca dung
mi.
1.2.2. in li v hng s in li.
c trng nh lng cho s phn li ca cc cht in li ngi ta da vo
in li v hng s in li K.
1.2.2.1. in li
L t s gia s mol (n) ca cht in li thnh ion vi tng s mol (n 0 ) ca cht
tan trong dung dch:

n
(2.2)
no

Nu chia c hai s hng ca biu thc (2.2) cho th tch V ca dung dch th:

C phnli
Cchatdienli

V d 2.2: i vi cht in li MX phn li theo s (2.1) ta c:


y, [Mn+], [Xn-], l nng tng ng ca cc ion Mn+ v Xn- do MX phn
li ra.
T (2.4) ta thy nng cht phn li bng tch nng cht in li vi in
li
[Mn+] = [Xn-] = CMX
c cc gi tr giao ng t 0 n 1: 0

(2.5)

= 0 i vi cht khng in li
= 1 i vi cht in li hon ton.
1.2.2.2. Hng s in li:
p dng nh lut tc dng khi lng cho cn bng (2.1) ta c:
KC

M X
MX (2.6)

y, [i] ch nng ca cu t i trong dung dch trng thi cn bng.


Kc l hng s in li nng , ph thuc vo bn cht cht in li, vo dung mi,
vo nhit . Trong dung dch long Kc khng ph thuc vo nng cht in li.
Thay (2.5) vo (2.6) v ch rng:
[MX] = CMX [Mn+] = CMX CMX = C(1 )
[6]

Ta c:

2C 2
KC
C 1

Vi 1 th

KC
C

2
KC

1
C

(2.7)

(2.8)

T biu thc (2.8) ta thy:


- in li t l thun vi hng s phn li K. Nu hng s phn li cng ln th cht
in li cng mnh, phn li cng nhiu. Nu K cng b th cht in li cng yu, cng t
phn li.
- in li t l nghch vi nng . i vi mt cht nht nh (K khng i )
th trong dung dch cng long th cht in li phn li cng nhiu.
1.2.3. Phn loi cht in li:
1.2.3.1. Cht in li mnh v cht in li yu:
Cn c vo in li v hng s in li m ngi ta qui c phn bit ra cc cht
in li mnh v cc cht in li yu.
- Mt s axit v c :HCl, HBr, HI, HSCN, HClO3, HBrO3, HNO3, H2SO4 (Nc1),
HClO4....
- Cc baz kim v kim th: LiOH, NaOH, KOH, RbOH, CsOH, FrOH,
Ca(OH)2, Sr(OH)2, Ba(OH)2 (nc 1).
- Hu ht cc mui.
Cc cht cn li thuc loi cht in li yu hoc trung bnh. H2O l cht in li
v cng yu.
1.2.3.2. Biu din trng thi cht in li trong dung dch:
c th ha mc phn li cc cht ngi ta qui c:
Cc cht in li mnh phn li hon ton , c biu din bng mt mi tn hng
t tri (ghi cng thc phn t ca cht in li) sang phi (ghi cng thc cc ion tng
ng). V d: Trong nc s phn li ca Na2SO4, HclO4, NaOH c biu din nh sau:
Na 2 SO4 2 Na SO42

HClO4 H ClO4
NaOH Na OH

Cc cht in li yu phn li mt phn, c biu din bng du cn bng thun


nghch ( ) gia cc phn t khng phn li v cc ion ca cht in li. c trng
nh lng hn ngi ta ghi thm gi tr K hoc lgK bn phi cn bng phn li.
V d 2.3: CH3COOH CH3COO- + H+ Ka = 10-4.76 hoc lgKa = -4,76
H2O H+ + OH-

Kw = 10-14 hoc lgKw = -14

Ag (NH 3 ) 2 Ag+ + 2NH3

K = 10-7.24 hoc lgK = -7.24

i khi ngi ta cng s dng i lng pK = -lgK. D nhin pK cng ln cht


[7]

in li cng yu, cng t phn li.


1.3. Nhng nh lut c bn tnh ton cn bng trong dung dch axit
baz
1.3.1. nh lut bo ton vt cht
1.3.1.1. nh lut bo ton nng
Qui c biu din nng trong dung dch:
Trong dung dch cc cht in li, nng cc cht thng c biu din theo
nng mol. Sau y l mt s qui c v cch biu din nng :
+ Nng gc C0: l nng cc cht trc khi a vo hn hp phn ng.
+ Nng ban u C0: l nng cc cht trong hn hp, trc khi phn ng
xy ra:
Cio

C oi .Vi
Vi

(3.1)

+ Nng ban u C: l nng cc cht sau khi phn ng xy ra hon ton


(nhng h cha t n trng thi cn bng). Trong trng hp khng c phn ng xy
ra th C v C0 ch l mt.
+ Nng cn bng [ ]: l nng cc cht khi h t n trng thi cn bng.
V d 3.1:Trn 200ml dung dch HCl pH =2 vi 300ml dung dch HNO3 pH =3.
y, nng gc: C0HCl = 10-pH = 10-2M, CoHNO3 = 10-pH = 10-3M
0
C HCl
Nng ban u: C HCl

200.10 2
4.10 3 M
200 300

0
C HNO
C HNO3
3

300.10 3
6.10 4 M
200 300

HCl H Cl
HNO3 H NO3

H2O H+ +OHBi v CHCl, CHNO3 >> 10-7 nn c th b qua s phn li ca nc. Nng cc cu
t lc cn bng:
[Cl ] = 4.10 -3 M, [ NO3-] = 6.10-4 M
[H+] = [Cl ] + [ NO3-] = 4,6.10-3 M
OH HK w 2,17.10 12 M
- nh lut bo ton nng (LBTN) ban u: y l dng ph bin
nht ca nh lut bo ton vt cht thng c p dng tnh ton cn bng trong
cc dung dch.
Pht biu nh lut: Nng ban u ca mt cu t bng tng nng cn
bng ca cc dng tn ti ca cu t c mt trong dung dch.
[8]

V d 3.2: Cho dung dch KH2PO4 nng C mol/l. Vit biu thc bo ton
nng ban u.
Cc qu trnh in li xy ra trong dung dch:

Biu thc LBTN i vi H 2 PO 4 :

V d 3.3: Vit biu thc LBTN i vi dung dch cha hn hp hai


mui NaHCO3 C1 v Na2CO3 C2 M.
Cc qu trnh in li xy ra trong dung dch:

Biu thc LBTN i vi HCO3- v CO32-:

LCO2: tan ca CO2


1.3.1.2. nh lut bo ton in tch:
LBTT c pht biu da trn nguyn tc cc dung dch c tnh trung ha v
in: Tng in tch m ca cc anion phi bng tng in tch dng ca cc
cation.

Trong ,

[i] : nng ca ion i lc cn bng


Zi : in tch ca ion i

V d 3.4: Vit biu thc LBTT cho dung dch KH2PO4 nng C mol/l
v d 3.2
Trong dung dch c cc ion: K+, H+, H2PO4-, HPO42-, PO43-, OH[9]

Biu thc LBTT:


1.3.2. nh lut tc dng khi lng
y l nh lut c p dng thng xuyn trong vic tnh ton cn bng trong
cc dung dch.
- Pht biu nh lut: trng thi cn bng t s gia tch ca nng cc
cht to thnh sau phn ng vi s m thch hp bng h s t lng ca n, trn
tch nng ca cc cht phn ng vi ly tha thch hp l mt hng s nhit
v p sut cho.
- Biu din LTDKL i vi mt s dng cn bng thng gp:
+ Cn bng axit-baz:
Cn bng phn li ca axit:

Ka l hng s phn li axit (hay gi tt l hng s axit).


Cn bng phn li ca baz:

Kb l hng s phn li baz (hay gi tt l hng s baz).


+ Cn bng to phc:

k1, k2 l hng s to thnh tng nc ca cc phc [CuNH3]+ v [Cu(NH3)2]+.

1, 2 l hng s to thnh tng hp ca cc phc [AgNH3]+, [Ag(NH3)2]+


+ Cn bng to hp cht t tan:
T PbCl2 l tch s tan ca PbCl2
-

Tng hp cn bng:

Trong thc t, chng ta thng gp nhng cn bng phc tp t nhng cn bng


[10]

ring l. Sau y l mt s v d tng hp cn bng:


+ Biu din cn bng theo chiu nghch:
Qu trnh thun:
Qu trnh nghch:
p dng LTDKL:

Nh vy, hng s cn bng nghch bng gi tr nghch o ca hng s cn


bng thun.
+ Cng cn bng:
Cho:
Tnh hng s cn bng:
Cn bng (3.4) l cn bng tng ca hai cn bng (3.2) v (3.3)

Hng
hp
khi
bng
vi
cc cn hng s ca cc cn bng ring l.

s cn bng t
cng
cc
cn
nhau bng tch

+ Nhn cn bng vi mt tha s n ( n= -2, -1, 1, 2, ,)


Khi nhn cn bng vi mt tha s n bt k s tng ng vi vic cng n ln
ca cn bng . Do , hng s ca cn bng t hp (hng s ca cn bng khi
nhn vi tha s n) bng hng s ca cn bng gc ly tha n ln.
V d 3.5: Khi nhn cn bng (3.2) vi tha s n, ta c cn bng t hp:
Hng s cn bng kn = K1n.

1.3.3. nh lut bo ton proton (iu kin proton)


y l trng hp ring ca LBTN v LBTT p dng cho cc h axitbaz:
Pht biu nh lut:
Nu chn mt trng thi no ca dung dch lm trng thi chun (mc khng)
[11]

th tng nng proton ca cc cu t mc khng gii phng ra bng tng nng


proton m cc cu t thu vo t n trng thi cn bng.
Ni cch khc, nng proton trong dung dch lc cn bng bng hiu gia
tng nng proton gii phng ra v tng nng proton thu vo mc khng.

Trng thi chun (mc khng) l trng thi ty chn (trng thi ban u,
trng thi gii hn, trng thi cn bng,...). thun tin cho vic tnh ton, ngi ta
thng chn mc khng l trng thi nng ca cc cu t chim u th.
V d 3.6: Vit biu thc KP cho dung dch KH2PO4 nng C mol/l v d
3.2
Chn mc khng: H2PO4- v H2O

V d 3.7: Vit biu thc KP


CH3COONa C2M.

cho dung dch CH3COOH C 1 M v

Mc khng: CH3COOH v H2O

KP:

1.4. Cn bng trong dung dch axit baz


1.4.1. Dung dch cc n axit baz
1.4.1.1. n axit mnh
Axit mnh (k hiu HY) nhng hon ton proton cho nc :
[12]

Trong dung dch: [HY] 0, [Y-] = CHY.


Cc axit mnh thng gp l :HCl, HBr, HI, HSCN, HClO3, HbrO3, HNO3, H2SO4
(Nc 1), HClO4....
Cn bng (4.1) thng c vit dng n gin:
Trong dung dch ngoi qu trnh phn li (4.2) cn c qu trnh phn li ca nc:
Nh vy c hai qu trnh cho proton v phng trnh KP c dng:

Hoc:
S c mt ca ion H+ do HY phn li ra lm chuyn dch cn bng (4.3) sang tri
v [OH ] < 10-7. V vy, trong trng hp CHY 10 -7 c th coi [H+] = CHY .
Ngha l, trong dung dch s phn li ca HY l chim u th cn s phn li ca
H2O xy ra khng ng k.
Trong trng hp CHY 10-7 th phi k n s phn li ca nc v php tnh
c thc hin n gin theo cn bng phn li ca nc.
V d 4.1:Tnh pH, H+, OH ca dung dch HCl 1,0. 10-3 M

Do CHCl 10-7 [H+] = CHCl = 1,0.10-3 pH = -lg(1,0.10-3) = 3,0


pOH = 14,0 pH = 14,0 3,0 = 11,0 [OH ] = 1,0.10-11.
1.4.1.2. n baz mnh
Cc baz mnh thng gp:LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Ca(OH)2,
Sr(OH)2, Ba(OH)2 (nc 1).
Trong dung dch baz mnh XOH c cc qu trnh :
- Cn bng ion ha ca nc:
- Cn bng thu proton ca XOH:
-T hp (4.4) v (4.5)

-Mt cch n gin c th vit cc qu trnh xy ra trong dung dch baz mnh:

[13]

iu kin proton:

Hoc:
y do s c mt ca OH- gii phng ra t (4.7) m cn bng phn li ca nc
(4.8) chuyn dch sang tri v [H + ] << 10-7 .V vy, nu CXOH >>10-7 th:
[OH-] = CXOH (4.11)
Ngha l nng OH- trong dung dch bng nng ca baz mnh.
Trong trng hp CXOH 10-7 th phi k n s phn li ca nc nh i vi
trng hp axit mnh.
V d 4.2 : Tnh pH, H+, OH , ca dung dch NaOH 1,0. 10-4 M

CNaOH 10 -7 nn:

1.4.1.3. n axit yu
Cc axit yu phn li mt phn v dung dch c phn ng axit. mnh ca cc
axit c c trng bng hng s phn li axit Ka hoc ch s ca hng s phn li pKa
= -lgKa . D nhin Ka cng ln hay pKa cng b th axit cng mnh.
Cc axit yu c th tn ti dng phn t,cation hoc anion.V d :
[14]

Axit phn t: HCN H+ + CNAxit cation: NH4+ H+ + NH3


Axit anion: HSO4- H+ + SO42-

Ka = 10-9,35 ; pKa = 9,35


Ka = 10-9,24 ; pKa = 9,24
Ka = 10-1,99 ; pKa = 1,99

Trng hp tng qut trong dung dch n axit yu HA c cc qu trnh sau:

Theo nh lut tc dng khi lng p dng cho (4.13) ta c:

Hay :

Tch s ion ca hai qu trnh :

Nu Kw Ka.CHA th s phn li ca nc xy ra khng ng k v c th tnh


thnh phn cn bng theo (4.13):

Gii
phng
cho php nh gi x
[A ].

trnh
tc

(4.18)
l [H+],

-4

V d 4.3 : Tnh pH ca dung dch NH4Cl 1,0. 10 M.

y KA.C = 10-4.10 -9,24 = 10 -13,24 do khng th b qua s phn li ca nc.


Chn mc khng: NH4+, H2O
KP: [H +] = [OH-] + [NH3]
[15]

Coi ta c gi tr gn ng ca [H+]

1.4.1.4. n baz yu
Mt phn cc baz yu thu proton ca nc v dung dch ca chng c phn ng
baz. Cc baz yu c th tn ti dng phn t, anion hoc cation:
Baz phn t: NH3 + H2O NH4+ + OHBaz cation: CaOH+ Ca2+ + OHBaz anion: CH3COO- + H2O CH3COOH + OH mnh ca cc baz yu ph thuc vo hng s baz Kb hoc ch s hng s
baz pKb = -lgKb .
Hng s Kb c t hp t hng s phn li ca nc v hng s phn li ca axit
tng ng.
i vi baz A-:

T t hp cc phn ng trn ta c:

Nh vy khi axit HA cng mnh (Ka ln) th baz tng ng cng yu (Kb b) v
ngc li .
Phn ng (4.19), c trng cho phn ng ca cc baz, phn nh cc qu trnh
thu proton ca nc trong cc dung dch baz yu. gii thch tnh baz ca Atheo thuyt Areniut phng trnh (4.19) c gi l phn ng thy phn ca A-.
Nh vy trong bt k dung dch baz no cng u c hai qu trnh.
Phn li ca nc: H2O H+ + OH-

Kw

Thu proton ca baz: A- + H2O HA + OHTrong trng hp tch s ion Kw = [H+][OH ] ca nc rt b so vi tch s ion
[16]

ca baz ([HA].[OH-] = Kb. [A-] Kb.Ca).


Kw << Kb.Ca (4.21)

Th c th tnh cn bng ch theo (4.19):

C th tnh d dng x t (4.22)


Trong trng hp iu kin (4.21) khng tha mn, ngha l th phi tnh n
cn bng phn li ca nc. Php tnh gn ng c thc hin d dng da trn
phng trnh KP.
V d 4.4 : Tnh pH ca dung dch NaCN 0,010 M.

Kb.CCN- = 10-4,65 . 10-2 = 10-6,65 >> Kw.


iu kin (4.21) hon ton tha mn.Ta c th tnh cn bng theo (1).

Vy [OH -] = x = 4,73.10-4
pOH = -lg(4,73.10-4) = 3,32 pH = 10,68
1.4.2. Dung dch ca cc hn hp axit baz
1.4.2.1. Hn hp axit mnh v axit yu
Trong dung dch axit mnh HY nng C1 mol/l v axit yu HA c nng C2
mol/l c cc qu trnh sau:
Phn li ca axit mnh HY: HY H+ + Y- (4.23)
Ion ha ca nc: H2O H+ + OH- Kw (4.24)
Phn li ca axit yu HA: HA H + + A -

K a (4.25)

y : CHA = C2; CH+ = CHY= C1


Trong a s trng hp, do c mt ca cc axit HY v HA nn s phn li ca nc
[17]
a

xy ra khng ng k.Ta c th tnh nng ion H+ da vo cn bng (4.25) c k n


s c mt ca ion H+ do HY phn li ra (4.23):

Nu hng s phn li KHA tng i b v C1, C2 khng qu nh th c th coi x


C2 ; x C1 v ta c th nh gi gn ng.

V d 4.5 :Trn 20,00ml HCl 0,0200M vi 30,00ml dung dch CH3COOH 0,150
M tnh pH ca hn hp thu c ?
CHCl = 20.0,02/(20+30) = 0,008 (M)
CCH3COOH = 30.0,15/(20+30) = 0,09 (M)
Cc cn bng xy ra trong dung dch:

Vi x 0,008 ta rt ra phng trnh gn ng:

Gi tr ny nh hn 0,008 khng nhiu .Nu coi x 0,090 th :


x2 +8.10-3x 1,566.10-6 = 0
tnh c: x = 1,912.10-4 0,090
Vy x = [CH3COO ] = 1,912.10-4
+
-4
-3
[H ] = 0,008 + x = 0,008 + 1,912.10 = 8,19.10
pH = 2,09
[18]

1.4.2.2. Hn hp baz mnh v baz yu


Trong dung dch c qu trnh phn li hon ton ca baz mnh (XOH) cn bng
phn li ca nc, qu trnh proton ha ca baz yu A-:

C th coi qu trnh phn li ca nc xy ra khng ng k do s c mt ca


nng OH- sinh ra t hai qu trnh (4.28) v (4.30)
Ta c th nh gi nng OH- da vo cn bng (4.30) c tnh n s c ca
nng OH- do XOH phn li ra, vi C OH- = CXOH = C1 v C A- = C2.

Vi x C1; x C2 ta c gi tr gn ng:

V d 4.6 :Tnh pH ca dung dch gm NaOH 1,0. 10-4 M v NaNO2 0,10 M

Vi x 1,0.10

-4

[19]

Vy x = [HNO2] = 10-7,71
[OH-] = 1,0.10-4 + x = 1,0.10 -4 + 10-7,71 = 10-4
pOH = 4,0 pH = 10
1.4.2.3. Hn hp n axit
Trong dung dch cha cc n axit HA1, HA2, HA3 c cc cn bng

Trong trng hp: Ka1CHA1>> Ka2CHA2 >> Ka3CHA3 >> Kw th c th tnh nng
ion H+ theo cn bng (4.33) nh i vi dung dch cha n axit.
Trong trng hp Ka1CHA1 Ka2CHA2 Ka3CHA3 th biu thc KP p dng cho h s
l:
+
Sau khi t hp cn thit vi ch [H ] [OH ] ta c:

tnh gn ng c th coi [H A1 ] CHA1= C1; [H A2 ] CHA2 = C2; [H A3 ] CHA = C3 v:


kim tra ta tnh li: [H A1 ] = C11; [H A2 ] = C22; [H A3 ] = C33 vi:

V d 4.7 : Tnh pH ca dung dch CH3COOH C1 = 0,010 M v NH4Cl C2 = 0,100M

Bi v Ka1C1 (10-6,76) Ka2C2 (10-10,24) > Kw nn c th tnh [H+] theo (3):

[20]

[H + ] = 4,17.10-4M; pH = 3,38
T cn bng (1): NH 3

0,10
.10 9, 24 10 6 ,86 << 10-3,38, vy s phn li ca NH4+
3, 38
10

l khng ng k i vi axit axetic.


1.4.2.4. Hn hp n baz
Vic tnh cn bng i vi hn hp cc n baz cng tng t nh hn hp
cc n axit.
Trong dung dch: NaA1 C1M ; NaA2 C2M

Nu K b1 C 1 K b2 C 2 K w th php tnh c thc hin theo cn bng (4.40).


Nu K b1 C 1 K b2 C 2 K w th phi tnh theo KP:
[H + ] = [OH - ] - [ HA1] - [HA2] (4.42)
Thay [HA1] = Ka1-1[H+][A1-] v [HA2] = Ka2-1[H+][A2-] vo (4.42) v khi t hp cn thit
ta rt ra:

Vi gi tr tnh gn ng :

V d 4.8 : Tnh pH ca dung dch KCN C1 = 0,100M ( pKa1 = 9,35 ) v NH3


C2 = 0,100M ( pKa2 = 9, 24 ).
[21]

K b1 C 1 K b2 C 2 K w . p dng (4.44) :

1.4.2.5. Hn hp n axit yu v baz lin hp


Xt dung dch n axit HA (Ca mol/l) v baz lin hp (Cb mol/l)

Hoc:
Cn bng (4.45) m t ng hin tng khi dung dch c phn ng axit. Nu pH
7 th c th tnh [H+] theo (4.45):

Trong trng hp h << Ca, Cb th h K a

Ca
v ta c cng thc gn ng tnh pH:
Cb

Nu pH 7 th cn bng (4.46) m t ng hin tng v c th da vo


tnh pH:

b
b
Khi x = [OH - ] << C a , C b th [OH - ] = x = K b C v pOH pK b lg C (4.48)
a
a

Thay pOH = 14 pH v pKb = 14 pKa vo (4.48) ta li c phng trnh tnh


pH nh (4.47). phng trnh (4.47) c gi l phng trnh Henderson
Hasselbalch hay c dng trong cc ti liu sinh hc v sinh ha tnh pH ca
cc dung dch m. Ch rng phng trnh ch ng khi pH khc nhiu vi 7,0 v
[22]

khi [OH ], [H+] Ca, Cb.


Khi khng th b cn bng phn li ca nc c th tnh gn ng theo phng
trnh KP p dng cho h HA (C ), A- (C ):
a

Kt qu tnh theo phng trnh gn ng: h2 + Cbh - (K w+ KaCa ) = 0 s cho ta


[H+] = h
V d 4.9:Tnh pH ca hn hp NH4+ C1 = 0,050M v NH3 C2 = 0070M pKa =
9,24.

Tnh gn ng :

pH 9,24 lg

0,070
9,38 ;
0,050

pOH = 4,62

[OH-] = 10-4,62 Ca, Cb vy gi tr pH tnh c l ng.


1.4.3. Dung dch cc a axit baz
1.4.3.1. a axit
Phn t ca cc a axit c kh nng phn li cho n proton (n>1). Nu n = 2 ta c
iaxit, n= 3 ta c triaxit..... S phn li ca cc a axit din ra theo tng nc. V d, s
phn li ca triaxit H3A:

i vi a s cc a axit nht l i vi cc axit v c th Ka1 Ka2 Ka3 ....,


ngha l s phn li ca a axit xy ra mnh nht nc u v sau gim dn cc nc
tip theo. iu ny d hiu v mt phn t khng mang in mt proton d hn mt
anion v anion mt in tch mt proton d nhin tng i d hn anion hai in
tch.....
Nu Ka1 Ka2 Ka3 ta c th coi a axit nh mt n axit v tnh cn bng theo
nc phn li th nht ca axit .
V d 4.10 :Tnh pH v nng ion S2- trong dung dch H2S 0,010M
Cc cn bng xy ra trong dung dch:

[23]

V Ka1 Ka2 Kw nn cn bng (1) l ch yu

Vi x << 0,010 x= 10 -4,51 << 0,010


Vy [H+] = [HS ] = 10 -4,51 pH = 4,51
tnh nng ca ion S2- ta dng cn bng 2 c k n nng cc ion
tnh c t trc :

Vi y 10-4,51 y = Ka2 = 10-12,9 10 -4,51 ,vy [S2-] = 10-12,9 bng ng gi tr


Ka2, khng ph thuc nng a axit.
1.4.3.2. a baz
Phn t a baz c kh nng nhn mt s proton .Qu trnh proton ha ca a
baz l ngc li vi qu trnh phn li ca a axit tng ng .V vy ng vi iaxit ta
c ibaz ,ng vi triaxit ta c tribaz ....v ta c s phn ng sau y:
Phn li ca triaxit
Proton ha ca tribaz

Khi Ka1 Ka2 Ka3 th Ka3-1 Ka2-1 Ka1-1 v vy Kb1 Kb2 Kb3.
Nh vy s proton ha nc 1 l chim u th v ta c th tnh cn bng ca a baz
nh mt n baz:

[24]

V d 4.11:Tnh H+, HCO3-, pH ca dung dch Na2CO3 0,10M


Cc cn bng xy ra trong dung dch:

Kb1 Kb2 Kw nn cn bng (2) l ch yu.

Kt qu tnh cho ta :[HCO3-] = [OH - ] = 4,62.10-3 ; pOH = 2,34 ; pH = 11,66


Phn 2 PHNG PHP TH LOGARIT GII BI TON Ph
2.1. Tnh ton cn bng trong cc dung dch axit:
2.1.1. Dung dch n axit mnh
Cc axit mnh thng gp l: HCl, HBr, HSCN, HClO3, HBrO3, HNO3, H2SO4,
HClO4, HMnO4
ng dng tnh pH, H+, OH- ca dung dch HCl 1,0. 10 -3 M
Cc cn bng xy ra trong dung dch:

Mc khng : HCl ; H2O


KP : [H+] = [Cl-] + [OH-]
Trong :

Ly logarit thp phn h trn ta c :

T nhng d liu trn ta v c th logarit nh sau:


[25]

Da vo gin ta thy ti v tr ct nhau gia hai ng lg[H+] v lg[Cl ] th


nng OH rt b so vi nng Cl . Vy khi tnh pH ca dung dch ta c th b
qua phng trnh phn li ca nc.
T phng trnh iu kin proton: [H+] = [Cl-] + [OH-]
[H+] = [Cl-] = 0,001 = 10-3
[OH-] = 10-14 / 10 -3 = 10-11
pH = - lgH+] = - lg10 -3 = 3
pOH = 14 pH = 14 3 = 11
2.1.2. Dung dch n axit yu:
Cc axit yu c th tn ti dng phn t hoc ion: HCN, CH3COOH, NH4+, HSO4-
Cc axit ny iu c hng s phn li axit (Ka) v cc qu trnh phn li trong nc
l nh nhau. Xt trng hp sau:
Tnh pH ca dung dch NH4Cl 1,0. 10-4 M.[4]
Cc qu trnh xy ra trong nc:

Chn mc khng: NH4+, H2O


KP: [H +] = [OH-] + [NH3]
Trong :
[26]

Ly logarit thp phn h trn .Ta c:

T nhng d liu trn ta v c th logarit nh sau:

Ta thy ti hai ng lg[H+] v lg[NH3] ct nhau th [OH ] l ng k so vi


[NH3] v vy khi tnh pH ca dung dch phi tnh c phng trnh phn li ca nc.
[H+] = [OH ] + [NH3]

Vi Ka = 10-9,24,Ta c:
[27]

Vy h = [H+] = 2,60.10 -7 pH = -lg[H+] = - lg(2,60.10-7) = 6,59


2.1.3. Hn hp axit mnh v axit yu
Xt trng hp sau: trn 20,00ml HCl 0,0200M vi 30,00ml dung dch
CH3COOH 0,150 M tnh pH ca hn hp thu c.
CHCl = 20.0,02/(20+30) = 0,008 (M)
CCH3COOH =30.0,15/(20+30) = 0,09 (M)
Cc cn bng xy ra trong dung dch:

Chn mc khng: CH3COOH, H2O


KP: [ H+]2,3 = [OH ] + [ CH3COO ]
[H+] - [Cl ] = [OH ] + [ CH3COO ]
[H +] = [OH ] + [ CH3COO ] + [Cl ]
Trong :

Ly logarit thp phn h trn. Ta c:

[28]

T nhng d liu trn ta v c th logarit nh sau:

T phng trnh KP :[Cl-] = const


pH ca dung dich ph thuc vo (2) v (3)
Ta thy ti v tr hai ng lg[H+] v lg[CH3COO-] giao nhau th nng [OH-]
rt nh so vi [ CH COO-] .Vy khi tnh pH b qua phng trnh phn li ca nc.
3

T phng trnh KP b qua [OH-] ,Ta c:


[H +] = [ CH3COO -] + [Cl-]
[29]

Trong Ka = 10-4,76 thay vo trn ta c:

h = [H+] = 8,16.10-3
pH = - lg[H+] = - lg(8,16.10-3 ) = 2,09
Vy pH ca hn hp gm 20,00ml HCl 0,0200M v 30,00ml dung dch
CH3COOH 0,150 M l 2,09
2.1.4. Hn hp n axit
Xt trng hp sau: Tnh pH ca dung dch CH3COOH C1 = 0,010 M v NH4Cl
C2 = 0,100M [4]

Chn mc khng: CH3COOH


KP: [H +] = [OH-] + [ CH3COO-] + [NH3]
Trong :

Ly

logarit

thp phn h trn .Ta c:

[30]

T nhng d liu trn ta v c th logarit nh sau:

Ta thy ti lg[CH3COO ] = lg[H+] th [OH ] v [NH3] nh hn rt nhiu so vi


[CH3COO ].V vy khi tnh pH ca dung dch c th b qua phng trnh (1) v (2)
T phng trnh KP, suy ra : [H+] = [ CH3COO-]

Vi Ka2 = 10-4,76, ta c :
[31]

+
h = [H ] = 4,08.10-4
pH = - lg[H+] = - lg(4,08.10-4) = 3,39
Vy pH ca dung dch CH3COOH C1 = 0,010 M v NH4Cl C2 = 0,100M l 3,39
2.1.5. a axit
Cc a axit gm: H3PO4, H2CO3. H2S. . .
Xt trng hp sau: tnh pH v nng ion S2- trong dung dch H2S 0,010M.

Cc cn bng xy ra trong dung dch:

Mc khng: H2S , H2O


+

KP: [H ] = [OH ] + [ HS ] + [S2-]


Trong :

Ly logarit thp phn h trn. Ta c:

[32]

T nhng d kin trn ta v c th logarit nh sau:

Ta thy ti v tr lg[ HS-] = lg[H+] th [OH-] v [S2-] nh hn rt nhiu so vi [


HS-]. V vy khi tnh pH ca dung dch b qua (2) v (3)
[33]

T phng trnh KP, suy ra : [H+] = [HS ]

Vi Ka1 = 10-7,02 ; Ka2 = 10-12,09

h = [H+] = 3,09.10-5
pH = - lg[H+] = - lg(3,09.10-5) = 4,51
Vy pH ca dung dch H2S 0,010M l 4,51

2.2. Tnh ton cn bng trong cc dung dch baz:


2.2.1. Dung dch n baz mnh
Cc baz mnh thng gp: LiOH, NaOH, KOH, RbOH, CsOH, FrOH,
Ca(OH)2, Sr(OH)2, BaOH)2 (nc 1).
Xt trng hp: tnh pH, H+, OH-, ca dung dch NaOH 1,0. 10-4 M [4]
Cc cn bng xy ra trong dung dch:

Mc khng: H2O
KP: [H +] = [OH ] CNaOH
Trong :

[34]

Ly logarit thp phn h trn .Ta c:

T nhng d liu trn ta v c th logarit nh sau:

Ta thy [H+] nh hn rt nhiu so vi [Na+].Vy khi tnh pH ca dung dch ta c


th b qua phng trnh phn li ca nc
T phng trnh KP, suy ra: [H+] + CNaOH = [OH ]
[OH ] = CNaOH = [Na+] = 10-4
[H+] = 10 -14 /[OH ] = 10-14 /10 -4 = 10-10
pH = - lg[H+] = - lg10-10 = 10.
2.2.2. Dung dch n baz yu:
Cc baz yu gm: NH3, CaOH+, CH3COO . . .
V d: tnh pH ca dung dch NaCN 0,010 M [4]
Cc cn bng xy ra trong dung dch:

Mc khng: H2O
KP: [H+] = [OH-](3)
[35]

[H +] = [OH-] - [HCN]
Trong :

Ly logarit thp phn h trn. Ta c:

T nhng d liu trn ta v c th logarit nh sau:

T phng trnh KP,suy ra : [H +] + [HCN] = [OH ] (*)


Ta thy ti v tr ng lg[OH-] v lg[HCN] ct nhau th [H+] rt b so vi
[HCN]. Vy khi tnh pH ca dung dch c th b qua phng trnh phn li ca
[36]

nc.
T (*) : [HCN] = [OH-]

Vi Ka = 10-9,35 ,ta c:

[H+] = h = 2,16.10-11
pH = -lg[H+] = -lg(2,16.10 -11) = 10,67
Vy pH ca dung dch NaCN 0,010 M l 10,67

2.2.3. Hn hp baz mnh v baz yu


Xt v d nh sau: Tnh pH ca dung dch gm NaOH 1,0. 10 -4 M v NaNO2 0,10
M [4]

Mc khng: H2O
KP:

[H ] = [OH ] - [HNO2] - CNaOH

Trong :

[37]

Ly logarit thp phn h trn .Ta c:

T nhng d liu trn ta v c th logarit nh sau:

[38]

T phng trnh KP ,suy ra: [H+] + [HNO2] + CNaOH = [OH ] (*)


T gin ta thy ti v tr lg[Na+] ct lg[OH ] th [H+] v [HNO2] rt b so vi
[Na+]. Vy khi tnh pH ca dung dch c th b qua phng trnh (3) v (4).
T (*) C
= [OH-]
NaOH

Vy pH ca dung dch NaOH 1,0. 10-4 M v NaNO2 0,10 M :


pH = -lg[H+] = -lg(10-10) = 10
2.2.4. Hn hp n baz:
Xt trng hp sau: Tnh pH ca dung dch KCN C1= 0,100M (pKa1 = 9, 35) v
NH3 C2 = 0,100M (pKa2 = 9, 24) [4]
Cc cn bng xy ra trong dung dch:

Mc khng: H2O
KP: [H +] = [OH ] - [HCN] - [NH4+]
Trong :
[39]

Ly logarit thp phn h trn .Ta c:

T nhng d liu trn ta v c th logarit nh sau:

T phng trnh KP,suy ra: [H+] + [HCN] + [NH4+] = [OH ] (*)


[40]

Ta thy ti lg[HCN] = lg[OH ] th [NH4+] gn bng [HCN] v [H+] nh hn rt


nhiu so vi [HCN].Vy khi tnh pH ca dung dch c th b qua phng trnh phn
li ca nc.
T (*) [HCN] + [NH4+] = [OH ]

Vi Ka1 = 10-9,35 v Ka2 = 10-9,24, ta thy Ka1 Ka2 >> h


(Ka1 + h) Ka1; (Ka2 + h) Ka2. Thay vo (**) ta c:

pH = - lg[H+] = - lg(5,0.10-12) = 11,30


Vy pH ca dung dch KCN C1 = 0,100M v NH3 C2 = 0,100M l 11,30
2.2.5. a baz
Xt v d: Tnh H+ , HCO3- , pH ca dung dch Na2CO3 0,10M [4]
Cc cn bng xy ra trong dung dch:

Mc khng: H2O
+

KP : [H ] = [OH ] - 2[H2CO3] - [HCO3-]

Trong :

[41]

Ly logarit thp phn h trn. Ta c:

T nhng d liu trn ta v c th logarit:

T phng trnh KP ,suy ra :[H+] + 2[H2CO3] + [HCO3-] = [OH-] (*)


[42]

T gin ta thy ti lg[HCO3-] = lg[H+] th [H+] v 2[H2CO3] nh hn rt nhiu so


vi [HCO3-]. Vy khi tnh pH ca dung dch c th b qua cn bng phng trnh
(3) v (4).
(*) [HCO3-] = [OH-]

Vi Ka1 = 10-6,35 ; Ka2 = 10-10,33 ,ta c:

Vy pH ca dung dch Na2CO3 0,10M l 11,66


2.3. Hn hp n axit yu v baz lin hp
Xt v d: tnh pH ca hn hp NH4+ C1 = 0,050M v NH3 C2 = 0,070M
Cc cn bng xy ra trong dung dch:

KP : [H ] = [OH ] + [NH3] C2
Trong :

Ly logarit thp phn h trn .Ta c:


[43]

T nhng d liu trn ta v c th logarit nh sau:

T phng trnh iu kin proton [H+] + C2= [OH-] + [NH3] (*)


T gin ta thy ti lgC2 ct lg[NH3] th [OH-] v [H+] rt nh so vi [NH3].
Vy khi tnh pH ca dung dch c th b qua phng trnh phn li ca nc [OH-].
[H+].
(*) C2 = [NH3]

Thay Ka = 10 -9,24 vo phng trnh trn ta c:

[44]

[H+] = h = 4,11.10-10
+
pH = -lg[H ] = -lg(4,11.10 -10) = 9,386
Vy pH ca hn hp NH4+ C1 = 0,05M v NH3 C2 = 0,070M l 9,39.

Phn 3 KT LUN
[45]

Trn c s cc s liu v cc ti liu tham kho v cc cn bng trong dung dch


axit baz, cc hng s cn bng axit, baz v s dng phng php th logarit nhm
chng em :
- Tnh v v gin logarit nng .
- p dng tnh ton cn bng trong cc dung dch axit baz. Kt qu cho thy
vic tnh ton tr nn d dng v khoa hc hn.

Phn cng nhim v:


H Th Ln
Nguyn Minh Khi

Tm ti liu, nh my.
Tm ti liu.

[46]

TI LIU THAM KHO


3. Nguyn Duy i.Mt s phn ng trong ha v c.NXBGD.Nm 2005.
4. Nguyn Tinh Dung . Ho hc phn tch 1. Cn bng ion trong dung dch. NXB
HSP, H Ni, 2005.
5. Nguyn Tinh Dung, o Th Phng Dip. Ho hc phn tch . Cu hi v
bi tp. Cn bng ion trong dung dch. Gio trnh cao ng s phm, NXB HSP,
H Ni, 2005.
6. Ren Didier. Ha i cng, Tp 2, NXBGD, H Ni, 1996

[47]

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