1

Chng 11. ng chun nhng h Axit

Baz phc tp
Lm Ngc Th
C s ha hc phn tch. NXB i hc quc gia H Ni 2005.

T kho: ng chun , C s ha hc phn tch, Dung dch a axit, Hm s ca

ph, Cht in li lng tnh, a axit, a baz.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc

ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 11 ng chun nhng h Axit Baz phc tp.......................................... 2
11.1 ng chun hn hp axit mnh v axit yu hoc hn hp baz mnh v baz
yu ................................................................................................................................... 2
11.2

Tnh ton nng cn bng ca cc h a axit - a baz ....................................... 5

11.2.1 Dung dch mui loi NaHA ................................................................................... 6

11.2.2 Dung dch a axit .................................................................................................... 9
11.2.3 Dung dch a baz................................................................................................. 12
11.2.4 Dung dch m ca cc h axit yu v baz lin hp vi n ............................. 13
11.3

ng chun a axit........................................................................................... 15

11.4

ng chun a baz......................................................................................... 21

11.5

ng chun cht in li lng tnh ................................................................. 23

11.6

Thnh phn ca dung dch a axit l hm s ca pH ............................................ 25

Chng 11
ng chun nhng h Axit Baz phc tp
Trong chng ny chng ta s xem xt nhng cn bng c thit lp trong dung dch c
hai axit hoc hai baz khc nhau v hng s phn li. ng ch l hai loi dung dch:
Dung dch hn hp n axit hoc n baz;
Dung dch hn hp a axit hoc a baz.

11.1 ng chun hn hp axit mnh v axit yu hoc hn hp baz

mnh v baz yu
Xy dng ng chun hn hp axit mnh v axit yu c thc hin trn v d chun
hn hp axit clohiric v axit yu HA.
giai on u ca php chun , nng ion hiro c din t bng phng trnh:
[H3O+] = CHCl + [A] + [OH]
trong s hng u th hin s ng gp ca axit mnh, s hng th hai l s ng gp
ca axit yu, s hng th ba l s ng gp do s phn li ca dung mi vo axit tng cng
ca dung dch. Trong phn ln cc dung dch axit, s ng gp do s phn li ca dung mi
qu nh nn c th b qua trong cc php tnh.
giai on u ca php chun, axit clohiric ngn cn s phn li ca axit yu nn c
th chp nhn [A] << CHCl v do nng ion hiro ca hn hp bng nng ca axit
mnh.
V d: Tnh pH ca dung dch c [HCl] = 0,120 M v [HA] = 0,080 M (Ka=1,00.104)
[H3O+] = 0,120 + [A]
Gi thit rng [A] << 0,120, khi [H3O+] = 0,120 v pH = 0,92. kim tra ng
n ca gi thit trn ta tnh nng [A]:

3
A
1,00.104
= Ka
=
= 8,33.104
+
HA
0,120
[ ] H3O

V:
0,080 = CA = [HA] + [A]
nn:
A
0,080 = + A
8,33.104

T :

[A] = 6,66.105 mol/l

R rng l [A] << 0,120, ngha l gi thit nu trn l ng.

Nh vy l, c th dng nhng gi thit tng t cho ti khi chun ht phn ln axit
mnh. T ta thy r, phn u ca ng chun hn hp axit mnh v axit yu khng
khc ng chun ring dung dch axit mnh. Tt nhin s c mt ca axit yu HA cn
phi c k n trong trng hp nng axit mnh thp.
V d: Tnh pH ca dung dch to thnh khi thm 29,00 ml dung dch NaOH 0,100 M vo
25,00 ml dung dch c [HCl] = 0,120 M v [HA] = 0,080 M (Ka = 1,00.104).
Tnh nng HCl v HA sau khi thm dung dch NaOH:
25,00 0,120 29,00 0,100
= 1,85.103 M
54,00
25,00 0,080
=
= 3,70.102 M
54,00

CHCl =
CHA

nn:
[H3O+] = CHCl + [A] = 1,85.103 + [A]

(11.1)

Ngoi ra ta c th vit:
CHA = [HA] + [A] = 3,70.102 M

(11.2)

Bin i phng trnh hng s phn li axit c th tm c [HA]:

H3 O+ A

[HA ] =
1,00.104

Gii ng thi hai phng trnh cui ta c:

(11.3)

4
H3 O+ A

+ A = 3,70.102

1, 00.104

T ta tm c:
3,70.106
A =
H O+ + 1,00.104
3

Thay [A] v CHCl vo phng trnh (11.1) ta c:

3,70.106
H3 O+ = 1,85.103 +

H O+ + 1,00.104
3

hoc:

[H3O+]2 1,85.103[H3O+] 3,88.106 = 0

[H3O+] = 3,03.103 mol/l; pH = 2,52

Nh vy l, trong tng s nng H3O+ ca dung dch (3,03.103 M), phn ng gp ca

axit mnh l 1,85.103, phn ng gp ca axit yu l 1,18.103 M, hon ton c th snh vi
s ng gp ca axit mnh.
Nu lng baz thm vo tng ng vi lng axit clohiric ban u th dung dch thu
c v mi mt ng nht vi dung dch c pha ch bng cch ho tan mt lng axit yu
v natri clorua tng ng vo mt lng nc thch hp. Natri clorua khng nh hng n
pH ca dung dch v c th b qua nh hng ca lc ion ti nng ion hiro xy dng
phn tip theo ca ng chun c tnh ton tng t nh khi xy dng ng chun
axit yu long HA.
Do , dng ca ng chun hn hp axit mnh v axit yu ch yu ph thuc vo
hng s phn li (cng ) ca axit yu. Trn hnh 11.1 dn ra nhngng chun hn hp
axit mnh v axit yu khc nhau v hng s phn li. Ta nhn thy rng, nu hng s phn li
ca axit yu tng i ln (ng cong s 1), trn ng chun thc t khng c bc
nhy im tng ng th nht. i vi nhng hn hp nh vy, trn c s kt qu chun
ch c th xc nh tng nng axit (ngha l [HCl] + [HA]). Trong trng hp hng s
phn li ca axit yu qu nh th trn ng cong chun hn hp axit mnh v axit yu
cng ch c mt bc nhy. Nhng trong trng hp ny ch chun c axit mnh. Khi
chun hn hp axit mnh v axit yu c gi tr hng s phn li trung gian th trn ng
chun xut hin hai bc nhy ring bit. ng chun ca php chun hn hp
baz mnh v baz yu iu kin ca hng s phn li ca baz yu < 104 nhng >108
cng c hai bc nhy ging nh trng hp chun hn hp axit mnh v axit yu m
t trn y.

Hnh 11.1
Cc ng chun hn hp axit mnh v axit yu c hng s phn li axit hc nhau bng dung dch NaOH 0,100 M

Mi ng chun tng ng vi php chun 25,00 ml dung dch

c [HCl] = 0,120 M v nng axit yu HA l 0,080 M.

11.2 Tnh ton nng cn bng ca cc h a axit - a baz

Nhiu axit yu c kh nng tch ra hai hoc mt s ln hn proton. Chng ta xt cn
bng ca axit photphoric trong dung dch nc:
H3PO4 + H2O U H3O+ + H2PO4 ;

H3 O + H 2 PO4

= 7,11.10 3
K1 =
[H3 PO4 ]

H2PO4

H3O+ HPO42

= 6,34.108
K2 =

H2PO4

H3O+ PO34

= 4,2.1013
K3 =
HPO24

HPO24

+ H2O U H3O + HPO4

+ H2O U H3O +

PO34

i vi axit photphoric, cng nh i vi phn ln cc axit khc, mi hng s tip sau

lun nh hn hng s trc, ngha l K3 < K2 < K1.

Cng thng gp c cc a baz. Ion cacbonat l baz lin hp ca ion

bicacbonat tham gia vo cc cn bng tng nc sau:
CO32

HCO3

+ H2O U

HCO3

+ OH

+ H2O U H2CO3 + OH

( K b )1

HCO3 OH

= 2,13.104
=
CO32

( K b )2 =

[H2CO3 ] OH
HCO3

= 2,25.108

C th thu c gi tr bng s ca nhng hng s phn li baz ca CO32 v HCO3

((Kb)1 v (Kb)2 tng ng) xut pht t nhng hng s phn li tng nc ca axit cacbonic
(chng 4):

( K b )1 =
( K b )2 =

K H2O

( K a )2

K H2O

( K a )1

y (Ka)1 v (Ka)2 l nhng hng s phn li th nht v th hai ca H2CO3.

C th tnh ton kh chnh xc pH ca cc dung dch a axit v cc dung dch m ca cc
a axit bng cch s dng bin php i vi cc h a cu t c m t trc y (chng
4). Nhim v i hi phi gii mt s phng trnh kh vt v. Nhng trong nhng trng
hp khi m t s nhng hng s phn li axit hoc baz tng nc khong 103 hoc ln hn th c
th thc hin mt s gi thit nhm n gin ha kh nhiu php tnh. Tip theo chng ta s
xem xt nhng v d trong nhng gi thit c ng dng thnh cng. Phng php tng
qut tnh pH ca cc dung dch c xem xt trng hp dung dch mui loi NaHA.

11.2.1 Dung dch mui loi NaHA

Trong dung dch mui loi NaHA c kh nng th hin c tnh axit c tnh baz.
Phngtrnh phn li axit i vi NaHA c vit nh sau:
HA + H2O U A2 + H3O+
V HA l baz lin hp ca axit H2A nn cn bng th hai c thit lp:
HA + H2O U H2A + OH
mt trong hai phn ng ny, ion hiro c to thnh, cn trong phn ng cn li ion
hiroxyl c sinh ra. Dung dch HA s l axit hoc baz ty thuc vo t s hng s cn
bng ca hai qu trnh :

7
H3 O+ A 2

K2 =
HA
[ ]

Kb =

K H2O
K1

(11.4)

[H2 A ] OH

(11.5)

HA

Nu Kb > K2, dung dch s kim, cn trong trng hp ngc li dung dch s axit. Cht
loi NaHA c kh nng th hin c tnh axit v tnh baz c gi l cht in li lng tnh.
i vi dung dch NaHA ta c phng trnh cn bng vt cht:
CNaHA = [H2A] + [HA] + [A2]

(11.6)

v iu kin trung ho in:

[Na+] + [H3O+] = [HA] + 2[A2] + [OH]
V nng ion natri bng nng chung ca mui nn c th chuyn phng trnh cui
cng thnh:
CNaHA = [HA] + 2[A2] + [OH] [H3O+]

(11.7)

Thng thng i vi cc dung dch cc cht loi NaHA, khng nn b qua nng ion
hiroxyl v nng ion hiro. Do tm c gi tr ca tt c cc n s ([H3O+], [HA],
[A2], [OH]) cn phi gii h 5 phng trnh. V vy cn c tch s ion nc:
K H2O = H3O+ OH

Tm phng trnh chnh xc tnh [H3O+] suy ra t 5 phng trnh nu trn rt phc tp
nhng c th thc hin php gn ng chnh xc tnh pH ca cc dung dch ca phn
ln cc mui loi NaHA. Gii ng thi cc phng trnh (11.6) v (11.7) ta c:
[H2A] = [A2] + [OH] [H3O+]
Thay th cc gi tr [H2A] v [A2] bng cc phng trnh biu din qua [HA] nh cc
phng trnh (11.4) v (11.5) vo cc phng trnh trn ta s thu c:
K H2O HA K 2 HA

+ OH H O+

+
H3 O
K1 OH

v v

8
K H2O
OH =

H O+
3

nn
H3 O+ HA K 2 HA

+ K H2O H O+
3

K1
H3 O+
H3 O+

Sau khi nhn 2 v ca phng trnh vi [H3O+] v bin i:

HA

+ 1 = K HA + K
H3O
H2O
2

K1

+ 2

v t ta tm c gi tr cn tm:
H3 O+ =

K1K 2 HA + K1K H2O

HA + K1

(11.8)

Trong phn ln trng hp, c th chp nhn:

[HA] CNaHA

(11.9)

v do c th chuyn phng trnh (11.8) thnh dng:

H3 O+ =

K1K 2CNaHA + K1K H2O

CNaHA + K1

(11.10)

Phng trnh (11.9) c ngha trong iu kin hai hng s cn bng K1 v K2 nh v nng
NaHA khng qu nh.
Thng CNaHA >> K1 v K1K H2O << K1K2CNaHA nn phng trnh (11.10) c rt gn:
H3 O+ K1K 2

(11.11)

Rt ng ch l, c mt khong nng m pH ca dung dch mui loi NaHA

khng ph thuc vo nng .
V d 1: Tnh nng ion hiro trong dung dch NaHCO3 0,100 M.
Trc ht ta cn kim tra nhng iu kin cn thit s dng phng trnh (11.11).
H2CO3 c K1=4,45.107 v K2=4,7.1011. R rng l, K1 nh hn CNaHA rt nhiu; K1K H2O =

4,45.1021 v K1K2CNaHA=2.1018. Do chng ta c th s dng phng trnh n gin

ha:
H3 O+ 4,45.10 7 4,7.1011 = 4,6.109 mol / l

V d 2: Tnh nng ion hiro trong dung dch Na2HPO4 0,001 M.

gii bi tp trong trng hp ny cn s dng hp l cc hng s phn li, K2 =
6,34.108 v K3 = 4,2.1013 ca H3PO4. Xem xt nhng iu kin s dng phng trnh
(11.11) ta thy rng, K1 = 6,34.108 nh hn rt nhiu nng Na2HPO4, do c th n
gin ha mu s. Mt khc, khng th b qua i lng K 2K H2O khi so snh vi
K2K3 CNa2HPO4 bi v thnh phn th nht l 6.1022 v thnh phn th hai l 3.1023. Nh vy
ta phi s dng phng trnh (10.11) dng n gin ha mu s:
8
13
1,0.103 + 6,34.1022
H3O+ = 6,34.10 4,2.10
= 8,1.1010 mol / l

1,0.103

Khi s dng phng trnh (11.11) ta thu c kt qu:

[H3O+] = 1,6.1010 mol/l.
V d 3: Tnh nng ion hiro trong dung dch NaH2PO4 0,0100 M.
Trong trng hp ny, K1 = 7,11.103 v K2 = 6,34.108 ca H3PO4 l nhng hng s cn
thit. K1 v CNaH2PO4 l nhng i lng khng khc nhau nhiu nn mu s ca phng
trnh (10.11) khng th n gin ha c, nhng v K1K2 CNaH2PO4 >> K1K H2O nn t s ca
phng trnh c n gin ha n K1K2 CNaH2PO4 v tm c gi tr ca n s l:
3
8
2
H3O+ = 7,11.10 6,34.10 1,0.10 = 1,6.105 mol / l

1,0.102 + 7,11.103

11.2.2 Dung dch a axit

S phn li ca iaxit H2A xy ra theo hai giai on:
H2A + H2O U H3O+ + HA
HA + H2O U H3O+ + A2
c m t bng cc hng s cn bng tng ng:

10
H3 O+ HA

K1 =
[H2 A ]

(11.12)

H3 O+ A 2

K2 =

HA

(11.13)

i vi dung dch axit H2A bit nng , phng trnh cn bng vt cht c th vit
di dng:
CH2 A = [H2 A ] + HA + A 2

(11.14)

v iu kin trung ho in:

[H3O+] [HA] + 2[A2] + [OH]

(11.15)

V dung dch l axit nn c th b qua s hng cui cng trong phng trnh (11.15).
Bn phng trnh i s c lp trn cho php tnh ton tt c cc gi tr ca cc n s:
[H3O+], [HA], [H2A], [A2]. Nhng nu t s K1/K2 ln th cn c kh nng n gin ha
tip theo, ngha l gi thit rng nhng ion hiro to thnh giai on phn li th nht ngn
cn s phn li giai on th hai n mc l c th b qua s phn li ny. Theo gi thit ,
[A2] trong cc phng trnh (11.14) v (11.15) s nh thua nhiu so vi [HA] v [H2A]. Nu
gi thit c thc hin, phng trnh (11.14) s tr thnh:
CH2 A [H2 A ] + HA

(11.16)

v phng trnh (11.15) c n gin n:

[H3O+] [HA]

(11.17)

Gii ng thi cc phng trnh (11.16), (11.17) v (11.12) s thu c:

2

H3 O+

= K1
CH2 A H3 O+

(11.18)

Phng trnh cui cng tng t phng trnh dn ra trc y, tnh nng ion
hiro trong dung dch n axit yu (chng 4) v cng ging nh trng hp c m t
trc y c th gii hon ton hoc gii theo cch n gin ha nu H3O+ << CH2 A .

S thch ng ca gi thit cho rng, s phn li giai on th hai ca H2A l tht s c

th b qua c minh chng bng cch thay th phng trnh (11.17) vo phng trnh K2
(11.13). Kt qu thu c: [A2] K2 c s dng so snh [A2] vi cc kt qu tnh ton

11

c i vi mi trng hp c th ca [H3O+] hoc [HA]. Trong trng hp tng qut, s

b qua phn li giai on hai ca H2A khi tnh ton nng ion hiro c th dn ti sai lm
ng k ch trong trng hp nu t s K1/K2 nh hoc dung dch axit qu long. Trong nhng
trng hp nh vy cn phi gii h t bn phng trnh.
V d 1: Tnh pH ca dung dch axit maleic 0,100 M.
Ta k hiu axit maleic l H2M v vit cc phng trnh phn li:
H2M

HM

H3O + HM

H3O + M

H3 O+ HM

= K = 1,20.102
1
[H2 M]

H3 O+ M2

= K = 5,96.107
2
HM

B qua s phn li ca H2M giai on 2 v s dng phng trnh (11.18) tnh [H3O+]
ta c:
2

H3 O+

= K1 = 1,20.10 2
+

0,100 H3 O

Hng s phn li th nht ca axit maleic ln n mc l phi gii hon ton phng trnh
bc 2 tm [H3O+].
[H3O+]2 + 1,20.102[H3O+] 1,20.103 = 0
[H3O+] = 2,92.102 = [HM]
pH = log2,92.102 = 1,54
chng minh rng, s phn li ca axit maleic giai on 2 trong nhng iu kin
cho tht s c th b qua ta thay [H3O+] = [HM] vo phng trnh K2:
H3O+ M2

= 5,96.107 ; M2 = 5,9.107

HM

Nh vy l, [M2] tht s nh thua nhiu so vi [HM] v gi thit a ra khng c th

dn ti sai s ng k trong tnh ton nng ion hiro.
V d 2: Tnh nng ion hiro trong dung dch H2SO4 0,0400 M.
Axit sunfuric phn li hon ton giai on th nht v ch phn li mt phn giai on th
hai. Nu b qua s phn li giai on th hai th nng ion hiro l:

12

[H3O+] = [ HSO4 ] = 0,0400 mol/l

Nhng tnh [ SO24 ] t phng trnh K2 trn c s gi thit ch r rng:
H3 O+ SO42

1,20.102
HSO4

R rng l khng th b qua gi tr [ SO24 ] khi so snh vi gi tr [ HSO4 ] nn i hi

phi gii chnh xc hn.
Nng ion hiro ca dung dch l do s phn li ca H2SO4 nn:
[H3O+] = 0,0400 + [ SO24 ]
[ SO24 ] = [H3O+] 0,0400
Do iu kin cn bng vt cht nn:
CH2SO4 = 0,0400 = [HSO4 ] + [SO24 ]

Hp nht v bin i hai phng trnh cui cng ta c:

[ HSO4 ] = 0,0800 [H3O+]
Thay cc gi tr [ SO24 ] v [ HSO4 ] vo phng trnh K2 s c phng trnh:

H3O+ H3O+ 0,0400

= 1,20.102
+

0,0800 H3O

Sau khi bin i phng trnh s thu c:

[H3O+]2 0,0280[H3O+] 9,60.104 = 0
[H3O+] = 0,0480 mol/l

11.2.3 Dung dch a baz

Tnh ton pH ca dung dch a baz c thc hin tng t nh m t i vi dung
dch a axit.
V d: Tnh pH ca dung dch natri cacbonat 0,100 M.

13

Cn thit phi xem xt cc cn bng sau:

CO32

HCO3

+ H2O

+ H2O

HCO3

+ OH

H2CO3 + OH

HCO3 OH

= 2,13.104
CO32

[H2CO3 ] OH
HCO3

= 2,25.108

Nu do kt qu ca phn ng th nht, lng OH to thnh ngn cn s phn li

theo phng trnh th hai th [H2CO3] << [ HCO3 ] v [H2CO3] << [ CO32 ]. Do :
[HCO3] = [OH]
CO32 = CNa CO [OH ] CNa CO
2
3
2
3

Thay th nhng gi tr [ HCO3 ] v [ CO32 ] vo phng trnh K1 ta c:

[OH]2 = 2,13.104.1.101 = 2,13.105
[OH] = 4,62.103 mol/l
Gi thit a ra khng dn n sai s ng k trong tnh ton pH:

[H2CO3 ] OH
HCO3

= 2,25.108

S tht l, [H2CO3] << [ HCO3 ] v [ CO32 ]. C th ni rng, gi thit a ra

( CO32 CNa2CO3 ) mang li sai s nh hn 5%.

11.2.4 Dung dch m ca cc h axit yu v baz lin hp vi n

T a axit yu v mui ca n c th iu ch hai loi dung dch m:
1. Dung dch m ca h axit yu t do H2A v baz lin hp vi n NaHA.
2. Dung dch m ca h axit NaHA v baz lin hp vi n Na2A.
V hng s phn li ca HA nh hn hng s phn li ca H2A nn pH ca dung dch m
h NaHA v Na2A lun ln hn pH ca dung dch m h H2A v HA.

14

xc nh chnh xc nng ion hiro ca mt h m bt k, cn thit lp s

phng trnh tng ng. Nhng tnh ton ch cn s dng nhng cn bng chim u th, v
vy cn n gin ha nhng cn bng khng chim u th. V d nh, trong dung dch m
H2A v NaHA ch cn ch ti s phn li ca H2A giai on th nht, b qua giai on th
hai. Trong trng hp ny c th tnh ton nng ion hiro tng t nh dung dch m ca
n axit yu v baz lin hp vi n (chng 10). Ging nh trc y, kim tra ng
ca gi thit a ra cn tnh nng A2 v so snh vi [H2A] v [HA].
V d: Tnh nng ion hiro trong dung dch m ca axit phtaleic 0,100 M (H2P) v
kali biphtalat 0,200 M (KHP).
Cn bng c bn c ngha quyt nh trong dung dch l:
H2P + H2O U H3O+ + HP

H3 O+ HP

= K = 1,12.103
1
[H2P ]

B qua s phn li ca H2P giai on th hai ngha l gi thit rng:

[P2] << [HP] v [P2] << [H2P]
nn
[H2P] CH2P = 0,100
[HP] CKHP = 0,200
v do :
3
H3 O+ = 1,12.10 0,100 = 5,60.104 mol / l

0,200

Tnh [P2] c thc hin bng cch thay th [H3O+] v [HP] vo phng trnh K2. Kt
qu tnh ton ch r rng gi thit a ra l hon ton ng n.
i vi dung dch m c iu ch t NaHA v Na2A th cn bng c bn l s phn li
ca H2A giai on hai v phng trnh:
HA + H2O U H2A + OH
c b qua. Nu c th gi thit rng, nng H2A nh n mc khng ng k so vi
nng HA v A2 th c th tnh ton nng ion hiro ging nh i vi nhng dung dch
m n gin, ngha l s dng hng s phn li th hai ca H2A. kim tra ng n ca
gi thit a ra cn so snh nng H2A vi nng HA v A2.
V d: Tnh nng ion hiro trong dung dch m kali biphtalat (KHP) 0,0500 M v kali
phtalat (K2P) 0,150 M.

15

Phng trnh phn li ca axit phtaleic giai on hai:

HP + H2O U H3O + P

H3 O+ P2

= 3,91.106
K2 =
HP

Gi thit rng, [H2P] << [HP] v [H2P] << [P2], ta c

[HP] CKHP = 0,0500
[P2] C K 2 P = 0,150
T :
6
2
H O+ = 3,91.10 5.10 = 1,30.10 6 mol / l
3
1,5.101

kim tra ng n ca gi thit th nht ta tnh gi tr gn ng ca [H2P] bng cch

thay vo phng trnh K1 nhng gi tr bng s ca [H3O+] v [HP]:
1,3.10 6 0,0500
= 1,12.103
[H2P ]

Do gi thit a ra l hon ton c th ng dng c. Nng H2P nh thua rt

nhiu so vi nng HP v P2, v c th b qua phn ng phn li ca baz HP.
Khng phi trong tt c mi trng hp u c th chp nhn trong mt dung dch ch
tn ti mt cn bng duy nht. iu dn n nhng sai lm rt ng k trong tnh ton pH
ca nhng dung dch m bao gm nhng a axit nu nng axit v baz lin hp qu nh
hoc l hng s phn li ca axit giai on 1 v giai on 2 gn nhau v gi tr. Trong nhng
trng hp nh vy cn thit phi lao ng nng nhc hn tnh ton chnh xc hn.

11.3 ng chun a axit

ng chun a axit c dng phc tp hn so vi tt c cc ng chun cp
trc y. Nu nhng hng s phn li khc nhau ln th c th quan st thy mt s bc
nhy trn ng chun . C th s dng cc bc nhy trong thc t nu pH trong vng
bc nhy bin i t ngt.
Nhng bin php c s dng xy dng ng chun c m t trc y
u thch ng i vi h a axit iu kin t s K1/K2 cao hn 103 mt cht. Nu t s K1/K2
thp hn gi tr , sai s, c bit l trong vng im tng ng th nht cao hn nhiu
gi tr c th chp nhn c, do nhng tnh ton khi gii nhng cn bng cn thit phi
chnh xc hn.

16

lm v d, chng ta xem xt cch tnh nng ion hiro nhng thi im

khc nhau trong php chun axit maleic - mt axit hu c, kp, yu - c cng thc H2C4H2O2.
Ta k hiu axit t do l H2M v vit cn bng phn li ca axit theo hai giai on:
H2M + H2O

H3O+ + HM

K1 = 1,20.102

HM + H2O

H3O+ + M2

K2 = 5,96.107

V t s K1/K2 c gi tr ln (2.104) nn giai on u ca php chun c th b qua

s phn li ca H2M giai on 2, ngha l:
[M2] << [HM] v [M2] << [H2M]
C th ni rng, gi thit a ra trn y khng dn ti nhng sai s ng k trong gii
hn mt vi phn mi mililit trong vng im tng ng th nht. Sau im tng ng
th nht, cn bng chim u th l cn bng phn li ca axit maleic giai on 2 v khi c
th gi nh rng, phn ng phn li ca baz HM:
HM + H2O U OH + H2M
khng th hin nh hng ng k n pH ca dung dch. Nh vy l, trong cc tnh ton
ta chp nhn [H2M] << [HM] v [M2].
V d: Xy dng ng chun 25,00 ml dung dch axit maleic 0,100 M bng dung
dch NaOH 0,100 M.
Gi tr pH ca dung dch axit maleic 0,100 M trc khi bt u php chun c
tnh trc y (xem v d 1, mc 11.2.2, dung dch a axit); pH =1,54.
Tnh pH ca dung dch sau khi thm 5,00 ml dung dch NaOH. Sau khi thm dung dch
kim, axit maleic cha b chun H2M v baz lin hp vi n HM to thnh dung dch m.
B qua s phn li ca HM v tnh pH ging nh trng hp ca dung dch m to thnh t
n axit yu. Ta tm c nng H2M ( CH2M ) cha b chun v nng ca baz lin hp
HM (CNaHM).

CH2M =
CNaHM

25,00 0,100 5,00 1,00

= 6,67.102 M
30,00
5,00 1,00
=
= 1,67.102 M
30,00

Nh cc phng trnh (11.9) v (11.10) ta tm c:

[H2M] 6,67.102 M
[HM] 1,67.102 M

17

Thay th cc gi tr tm c vo phng trnh K1 ta c [H3O+] = 4,8.102 mol/l. Do ,

gi thit [H3O+] << CH2M hoc CHM u khng ng nn cn thit phi s dng nhng
phng trnh (11.7) v (11.8) chnh xc hn:
[H2M] 6,67.102 + [H3O+] [OH]
[HM] 1,67.102 [H3O+] + [OH]
V dung dch l axit nn gi thit cho rng [OH]rt nh l hon ton ng n. Thay th
cc gi tr [HM] v [H2M] trn vo phng trnh K1:

H3O+ 1,67.102 + H3O+

K1 =
= 1,2.102
2
+
6,67.10 H3O

Sau khi bin i ta c:

[H3O+]2 + 2,87.102[H3O+] 8,00.104 = 0
v t
[H3O+] = 1,74.102 mol/l;
pH = 1,76
Bng cch tng t c th tnh pH tt c cc im ca vng m th nht.
im tng ng th nht: im tng ng th nht:
HM 25,00 0,100 = 5,00.102

50,00

R rng l, c th n gin ha t s phng trnh (11.10). Mt khc, nng HM

khng khc nhiu gi tr K1 nn
H O+
3

K1K 2CHM
K1 + CHM

1,20.10 2 5,96.107 5,00.102

5,00.10

+ 1,20.10

= 7,60.105 mol / l

pH = 4,12
Vng m th hai: Tip tc thm kim vo, mt dung dch m mi s hnh thnh, bao
gm axit HM cha chun ht v baz M2 lin hp vi n. Nu baz thm vo n lng
b qua phn ng ca HM vi nc to thnh OH (mt vi phn mi mililit), pH ca
dung dch c th tnh ton d dng t K2. Chng ta tnh pH ca hn hp khi thm 25,50 ml
dung dch kim lm v d:

18

CNa2M

( 25,50 25,00 ) 0,100

50,50

0,050
50,50

v nng chung ca NaHM s bng:

CNaHM

25,00 0,100 ( 25,50 25,00 ) 0,100

50,50

2,45
50,50

Thay nng NaHM v M2 bng cc gi tr bng s tm c trn y vo phng trnh

K2:
H O+ 0,050
3 50,50
2,45
50,50

= K 2 = 5,96.107

[H3O+] = 2,92.105 mol/l

im tng ng th hai: sau khi thm 50,00 ml dung dch NaOH 0,100 M vo 25,00
ml dung dch H2M 0,100 M ta thu c dung dch Na2M 0,0333 M. Trong h ny, phn ng
ca M2 vi nc l cn bng chim u th nn ch cn ch n cn bng m thi. Nh
vy l:
M2 + H2O U OH + HM
Kb =

K H2O
K2

1,00.1014
5,96.107

[OH] = 2,36.105 mol/l

pH = 14,00 (log2,26.105) = 9,37

19

Hnh11.2
ng chun 25,00 ml dung dch axit maleic (H2M) 0,100 M

Tnh pH sau im tng ng th hai: Tip tc thm kim vo, s phn li ca M2 s b

cn tr, do pH ca dung dch c tnh theo lng kim d thm vo.

Hnh 11.3
Cc ng chun 25,00 ml cc a axit bng dung dch NaOH 0,100 M

20
1. Dung dch axit photphoric 0,100 M

21
2. Dung dch axit oxalic 0,100 M
3. Dung dch axit sunfuric 0,100 M

ng chun dung dch axit maleic 0,100 M bng dung dch kim NaOH 0,100 M
c dn ra trn hnh 11.2. ng chun c xy dng trn c s nhng tnh ton
trong v d trn y. Nhng bc nhy tng ng vi php chun proton th nht v th hai
c phn chia rt r rng. V nguyn tc, nu chn ng ch th s xc nh c hoc mt
hoc c hai bc nhy khi chun axit maleic. Vi quan im thc t, s dng bc nhy
th 2 thun tin hn bi v s bin i pH trong vng im tng ng th hai c th
hin chnh xc hn.
Trn hnh 11.3 dn ra nhng ng chun 3 a axit khc. Nhng ng chun ny
ch r rng, bc nhy tng ng vi im tng ng th nht c th hin r trn hnh
v ch c quan st thy trong trng hp nu cc hng s phn li K1 v K2 ca a axit khc
nhau ln.
Trong trng hp ca axit oxalic (ng s 2) t s K1/K2 bng khong 1000, do trong
vng im tng ng th nht, im un ca ng cong c quan st thy nhng bc
nhy nh ti mc thc t khng th xc nh c bng ch th. Kt qu l, xc nh chnh
xc oxalic ch c th s dng im tng ng th hai.
ng cong 1 l ng chun l thuyt ca axit photphoric, mt axit phn li 3 nc.
Trong trng hp ny t s K1/K2 bng khong 105, ln hn gn 100 ln so vi t s ca
axit oxalic, do trn ng chun , hai bc nhy c xc nh chnh xc v mi bc
nhy u hon ton thch ng cho mc ch phn tch. Nu dng ch th chuyn mu trong
vng axit cho php chun th 1 mol axit tiu tn 1 mol kim. Nu ch th i mu trong vng
kim th s tiu tn 2 mol kim cho 1 mol axit. Khng nn chun proton th 3 ca axit
photphoric bi v hng s phn li giai on qu nh (K3 = 4,2.1013). Hiu ng m ca giai
on phn li th 3 ca axit photphoric khng ln nhng theo dng ng cong 1 trn hnh
11.3 ta thy, d sao i na hiu ng cng gy nn s gim pH r rt hn sau im tng
ng th hai so vi cc ng chun ca axit 2 nc (ng cong 2 v 3) trn hnh 11.3.
Nh vy l, nhng bc nhy tch bit trn ng chun a axit ch c quan st
thy khi t s 2 hng s phn li khng nh hn 104. Nu t s hng s phn li nh hn gi tr
nu trn th s bin i pH trong vng im tng ng th nht s rt nh v bc nhy
khng nn s dng xc nh chnh xc. Trong trng hp ny cn c nh ha im tng
ng th hai.

11.4 ng chun a baz

Xy dng ng chun a baz, ni chung, tng t cch xy dng ng chun
a axit. Chng ta xem xt cch xy dng ng chun dung dch natri cacbonat bng dung
dch axit clohiric. Trong dung dch natri caconat trong nc nhng cn bng sau y c
thit lp:

22
CO32 + H2O

HCO3 + OH ;

HCO3 + H2O

H2CO3 + OH ;

( K b )1 =

K H2O

( K a )2

( K b )2 =

= 2,13.104

K H2O

( K a )1

= 2,25.108

Phn ng din t tng tc ca ion cacbonat vi nc quyt nh pH ban u ca dung

dch. pH ca dung dch c tnh theo phng php m t mc 11.2.3. Sau khi thm
nhng phn axit u tin, dung dch m c to thnh t baz cha b chun CO32 v axit
lin hp HCO3 . Nng ion hiroxyl c tnh t phng trnh (Kb)1 hoc nng ion
hiro c tnh t phng trnh (Ka)2. im tng ng th nht, natri bicacbonat l hp
cht ch yu nn nng ion hiro trong dung dch c xc nh bng phng trnh (11.11).
Tip tc thm axit, dn ti s hnh thnh dung dch m mi t bicacbonat v axit cacbonic.
Nng ion hiroxyl tng ng c tm thy t phng trnh (Kb)2 hoc nng ion hiro
tng ng c tm thy t phng trnh (Ka)1. im tng ng th 2, dung dch bao
gm axit cacbonic v natri clorua. Nng ion hiro c tnh ton theo phng php thng
thng, ging nh trng hp cc n axit yu, s dng (Ka)1. Cui cng, nu thm d axit
clohiric, s phn li ca axit yu b cn tr ti mc, nng ion hiro thc t do nng axit
clohiric quyt nh. Trn hnh 11.4 dn ra ng chun dung dch natri cacbonat. Trn
ng cong xut hin 2 bc nhy, bc nhy th hai th hin chnh xc hn. iu c
ngha l, c th dng phng php chun axit - baz xc nh cacbonat v bicacbonat
khi chng cng tn ti. Php chun theo phenolphtalein cho php nh lng s mmol
cacbonat. Nu chun n i mu bromcrezol lc, lng axit tiu tn tng gp 2 ln (lng
milimol cacbonat cng vi s milimol ca bicacbonat trong dung dch b chun).

Hnh 11.4
ng chun 25,00 ml dung dch natri cacbonat 0,100 M bng dung dch axit clohiric 0,100 M

23

11.5 ng chun cht in li lng tnh

Nh ni trc y, trong cc dung mi thch hp, nhng cht in li lng tnh c kh
nng th hin c tnh cht axit yu v c tnh cht baz yu. Ty thuc vo iu kin c th
m tnh axit hoc tnh baz th hin mnh hn. C th chun dung dch cht in li lng
tnh bng baz mnh hoc axit mnh, v d nh trong dung dch ihirophotphat trong nc,
cc cn bng sau y c thit lp:
H2PO4 + H2O

U H3O + HPO24
+

K2 = 6,34.108

H2PO4 + H2O

U OH + H3PO4

Kb =

K H2O
K1

= 1,14.10 12

Kb qu nh nn khng th chun bng axit, ngc li K2 ln v do c th chun

thnh cng H2PO4 bng dung dch kim chun. Trong dung dch natri hirophotphat, phn
ng xy ra:
HPO24 + H2O

H3O+ + PO34 ;

K3 = 4,2.1013

nn khng th chun bng kim, nhng mt khc:

HPO24 + H2O

OH + H2PO4 ;

Kb =

K H2O
K2

= 1,58.10 7

nn c th chun HPO24 bng dung dch axit clohiric chun.

Cc amino axit n gin nht thuc loi cc cht in li lng tnh quan trng. Tnh cht
axit - baz ca chng l do trong phn t c c nhm chc axit v nhm chc baz. Trong
dung dch nc ca aminoaxit in hnh, v d glyxerin, ba cn bng quan trng sau y c
thit lp.
H2NCH2COOH U H3+NCH2COO

(11.19)

H3+NCH2COO + H2O U H2NCH2COO + H3O+ ; Ka = 2.1010

(11.20)

H3+NCH2COO + H2O U H3+NCH2COOH + OH ; Kb = 2.1012

(11.21)

Phng trnh u tin l mt bin dng ca phn ng axit - baz - phn ng axit - baz ni
phn - v v thc cht tng t phn ng ca axit cacboxilic vi cc amin:
R1NH2 + R2COOH U R1NH3+ + R2COO

(11.22)

Hng s ion ha ca nhng amin bo in hnh c c trng bng nhng i lng trong
khong 104 105. Hng s phn li ca phn ln axit cacboxilic cng nm trong khong . Do
, nhng cn bng (11.19) v (11.22) thc t chuyn dch v bn phi.

24

Cc ht amino axit mang ng thi c in tch dng v in tch m (phng

trnh 11.19) c gi l cc ion lng cc. T gi tr cc hng s cn bng (11.20) v (11.21)
th tnh cht axit ca ion lng cc glixin th hin mnh hn tnh baz v do dung dch
glixin c phn ng axit yu.
Khc vi cc ion ch c in tch dng hoc m, ion lng cc amino axit mang ng
thi c in tch dng v in tch m nn khng in chuyn ti c catt v ant trong in
trng. pH ca dung mi c nng dng anion v cation bng nhau, s in chuyn ca
amino axit trong in trng khng quan st thy. Gi tr pH c gi l im ng in
v l c tnh quan trng ca amino axit. C th d dng tm c im ng in khi bit
hng s phn li. V d nh i vi glixin:
H3 O+ H2NCH2COO

=K ;
a
+

H3 NCH2COO

OH H3+ NCH2COOH

=K
b
+

H3 NCH2COO

im ng in:
[H2NCH2COO] = [H3+NCH2COOH]
Chia Ka cho Kb ta thu c:
H3O+

= Ka
OH K b

Sau khi thay [OH] bng

K H2O
H3 O+

v bin i:

H3 O+ =

K a K H2O
Kb

i vi glixin, im ng in nm pH = 6,0:
10
H3O+ = 2.10
1.1014 = 1.106
12

2.10

Nhng gi tr Ka v Kb ca nhng amino axit n gin thng nh ti mc khng th xc

nh trc tip bng phng php chun axit - baz. Khi thm focmalehit vo h s xy ra
phn ng phong to nhm chc baz do c th chun sn phm bng dung dch baz
chun. V d nh, trong trng hp glixin:

25

H3+NCH2COO + CH2O U CH2=NCH2COOH + H2O

ng chun sn phm phn ng c dng c trng cho cc axit cacboxilic in hnh.

11.6 Thnh phn ca dung dch a axit l hm s ca pH

c th hnh dung mt cch r rng hn v s bin i thnh phn ca dung dch xy ra
trong qu trnh chun a axit, cch biu din lng tng i ca phn t axit t do v tt
c cc dng anion ca n di dng hm s ca pH l rt c ch. lm vic cn nh
ngha i lng i vi mi ht trng thi cn bng xut pht t nng chung ban u
ca a axit. V d, nng chung ban u ca axit maleic l CH2M . Khi , cn bng vt cht
s l:

CH2 M = [H2M] + [HM ] + [M ]

v theo nh ngha:
o

[H M]
= 2 ;
CH2M

HM
M2

; 2 =
=
CH2M
CH2M

R rng l, tng ca tt c cc gi tr i vi mt h bt k cn phi bng n v:

o + 1 + 2 = 1
Chng ta c th din t o, 1 v 2 qua [H3O+], K1, K2. Bin i cc phng trnh hng
s phn li ta c:
K H M
K K H M
HM = 1 [ 2 ] ; M2 = 1 2 [ 2 ]
2
+

[H3 O ]
H3 O+

Sau khi thay th cc gi tr [HM] v [M2] tm c trn y, phng trnh cn bng

vt cht c dng:
CH2M = [H2 M ] +

K1 [H2 M ]
+

[H3 O ]

K1K 2 [H2 M ]
H3 O+

v sau khi bin i:

[H2 M] =

CH2M H3O+

H3O+ + K1 H3O+ + K1K 2

26

Thay gi tr [H2M] va tm c vo phng trnh o ta c :

o =

H O+
3

H3O+ + K1 H3O+ + K1K 2

(11.23)

Bng cch tng t, c th tm c nhng gi tr khc :

1 =

2 =

K1 H3 O+

H3 O+ + K1 H3 O+ + K1K 2

K1 K 2
+ 2

H O
+ K1 H3O+ + K1K 2
3

(11.24)

(11.25)

Chng ta nhn thy rng, mu s trong tt c cc phng trnh l ng nht v nh vy

l, s tnh ton gi tr gi tr pH xc nh khng phi l cng vic phc tp. Ngoi ra, t
phng trnh (11.23) n (11.25) cn thy r, lng tng i ca mi dng bt k gi tr
pH c nh no cng khng ph thuc vo nng chung ca axit ( CH2M ).

Hnh 11.5
Thnh phn ca dung dch axit maleic (H2M) bin i theo pH

27

Ba ng cong biu din trn hnh 11.5 minh ha s bin i cc gi tr ca tt c cc

ht trng thi cn bng xut pht t axit maleic ph thuc vo pH. i chiu cc ng
cong vi ng chun axit maleic (hnh 11.2) ta s c hnh nh trc quan v s bin i
nng ca tt c cc dng ca H2M trong qu trnh chun . V d, t hnh 11.2, pH ca
dung dch axit maleic trc khi bt u chun phi bng 1,5. Theo hnh 11.5, gi tr pH
o khong 0,7, cn 1 ca HM bng khong 0,3. Do 2 thc t bng khng. Nh vy
l, pH 1,5 khong 70% axit maleic tn ti dng khng phn li cn 30% tn ti dng
HM. Theo mc thm kim vo, pH ca dung dch tng ln, im tng ng th nht
(pH = 4,12) ton b axit maleic tn ti dng HM (11). Khi thm tip tc kim vo, hp
phn HM gim xung v hp phn M2 tng ln. Hon ton r rng l, im t ti im
tng ng th hai (pH = 9,37) thc t ton b lng axit maleic chuyn thnh baz M2.