1

Chng10. L thuyt chun Axit Baz i

vi nhng h n gin
Lm Ngc Th

C s ha hc phn tch. NXB i hc quc gia H Ni 2005.

T kho: C s ha hc phn tch, Chun axit-baz, Cht ch th, ng chun ,

Sai s chun , Tnh ph, Dung dch m.

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 10 L thuyt chun Axit Baz i vi nhng h n gin........................ 3
10.1

Thuc th chun chun axit - baz................................................................. 3

10.2

Cht ch th chun axit - baz.......................................................................... 3

10.2.1 L thuyt v tnh cht ca cht ch th ................................................................... 4

10.2.2 Nhng loi ch th axit - baz ................................................................................. 5
10.2.3 Sai s chun vi cc ch th axit - baz............................................................. 9
10.2.4 Nhng yu t nh hng ti tnh cht ca ch th................................................. 9
10.3

ng chun axit mnh hoc baz mnh........................................................... 9

10.4.1 Chun axit mnh bng baz mnh.................................................................... 9

10.4.2 Chun baz mnh bng axit mnh.................................................................. 13
10.4

ng chun axit yu hoc baz yu................................................................ 13

10.4.1 Tnh pH ca dung dch cha mt cp axit - baz lin hp................................. 13

10.4.2 nh hng ca lc ion n cn bng axit - baz................................................ 17
10.4.3 Dung dch m ...................................................................................................... 19
10.4.4 ng chun axit yu...................................................................................... 26
10.4.5 ng chun baz yu.................................................................................... 32

Chng 10
L thuyt chun Axit Baz i vi nhng h
n gin

Chun axit - baz l vic xc nh im cui da trn s bin i pH t ngt quan st

thy gn im tng ng. Ging nh nhng trng hp chun khc, bn cht v nng
ca c cht b chun v cht chun quyt nh khong bin ii pH. la chn cht ch
th thch hp v xc nh sai s chun cn phi bit s bin i pH trong qu trnh chun
. Nh vy, ngha l cn phi bit ng chun trong phng php axit - baz c xy
dng nh th no.
Trong chng ny s xt nhng axit v baz n gin, chng phn li tch ra mt ion
hiro hoc mt ion hiroxyl. Trong chng 11 s bn ti nhng ng chun nhng axit
hoc baz nhiu nc v hn hp axit.
chun b cho nhng bn lun sp ti, sinh vin cn xem li nhng kin thc v axit,
baz v phng php tnh ton cn bng axit - baz (chng 4).

10.1 Thuc th chun chun axit - baz

Trong phng php chun axit - baz, cc axit hoc baz mnh lun lun c dng
lm thuc th chun bi v phn ng vi s tham gia ca chng xy ra hon ton hn so vi
phn ng vi s tham gia ca axit hoc baz yu. Cng nh trong php chun kt ta,
phn ng xy ra cng hon ton, hm s p bin i cng ln v cng d xc nh im cui.

10.2 Cht ch th chun axit - baz

Nhiu hp cht tng hp cng nh t nhin c mu khc nhau ty thuc vo pH ca dung
dch. Mt s trong cc cht t lu c s dng ch r tnh kim hoc tnh axit ca
nc. Chng cng quan trng c i vi nhng nh ha hc hin i trong vic dng chng
xc nh pH ca dung dch v pht hin im cui trong chun axit - baz.

10.2.1 L thuyt v tnh cht ca cht ch th

Nhng ch th axit - baz l nhng hp cht hu c biu l tnh axit yu hoc baz yu.
Phn ng phn li hoc lin hp ca cht ch th km theo s chuyn v cu to bn trong dn
ti s bin i mu. Chng ta a ra phn ng in hnh ca ch th axit - baz di dng sau:
H2O + HIn U H3O+ + In
(mu axit)

(mu kim)

hoc
In + H2O U InH + OH
(mu kim)

(mu axit)

Trong cc dung dch axit mnh, ch th dng HIn l dng chim u th, tng ng vi
"mu axit" v In s l "mu kim" ca n. Trong cc dung dch kim, cc ht In s chim u
th tng ng vi "mu kim" ca cht ch th .
Khi cn bng, nhng qu trnh c c trng bng nhng hng s:
Ka =

[H3 O+ ][In ]
[InH][OH ]
v K b =
[HIn]
[In ]

C th bin i nhng phng trnh nh sau:

Ka
[In ]
Kb
K [H O+ ]
[InH]
=
v
=
= b 3
[HIn] [H3O+ ]
K H2O
[In ] [OH ]

Khi pH bin i, dung dch cha cht ch th bin i lin tc thnh phn phn trm dng
mu ca mnh. Nhng mt ngi rt khng nhy vi nhng bin i . Thng mt dng
phi hn t 5 n 10 ln dng kia th ngi quan st mi nhn bit c mu ca n; tip tc
tng lng d ca dng s kh nhn bit. S bin i mu ca ch th ch c nhn bit
trong vng m mt dng hn dng kia 5 10 ln. Nh vy "s bin i mu" quan st
c phn nh s chuyn dch cn bng ca ch th. Xt HIn lm v d, c th ni rng, ch th
th hin mu axit hon ton ca mnh c ngi quan st nhn bit khi:
[In ] 1
[In ] 10

v mu hon ton kim khi

[HIn] 10
[HIn] 1

Bn trong khong c xc nh bng nhng i lng , mu l mu hn hp ca ch

th. Nhng gii hn bng s nu tt nhin phn nh tnh cht trung bnh ca ch th. Mt s
cht ch th bin i mu trong khong hp hn i vi nng dng axit v dng kim, mt
s khc li bin i trong khong rng hn. Hn na, kh nng ca ngi quan st phn bit
mu cng khng ng nht. Nhng ngi m mu khng phn bit c mt s sc thi mu.

Nu thay hai t s nng vo phng trnh hng s phn li ca ch th th c th tnh

khong nng ion hiro cn thit chuyn mu ch th. i vi mu hon ton axit:
[H3 O+ ][In ] [H3O+ ] 1
+
= K a [H3O ] = 10.Ka
=
[HIn]
10

v mt cch tng t i vi mu hon ton kim:

[H3O+ ] 10
K
= K a [H3O+ ] = a
10
1

thu c khong chuyn mu ca ch th chng ta tm logarit m ca c hai phng

trnh.
Khong pH chuyn mu ca ch th:
t log10Ka n log

Ka
= t 1 + pKa n (1) + pKa = pKa 1.
10

Nh vy, s chuyn mu ca ch th vi hng s phn li axit 1.105 c quan st thy

khi pH ca dung dch bin i t 4 n 6. D dng rt ra nhng h thc tng t vi ch th
loi kim.

10.2.2 Nhng loi ch th axit - baz

Danh sch nhng hp cht c tnh cht ch th axit - baz l danh sch nhng cht hu
c. Thng c th tm ch th c mu bin i trong khong pH cn thit bt k. Mt s ch
th c dn ra bng 10.1.
Bng 10.1 Mt s ch th axit - baz quan trng

Tn

Khong bin i pH

S bin i mu

Loi ch th
a

Dng axit

Dng kim

1,22,8

Vng

8,0 9,6

Vng

Xanh bin

Metyl vng

2,9 4,0

Vng

Metyl da cam

3,1 4,4,

Vng

Bromcresol lc

3,8 5,4

Vng

Xanh bin

Timol chm

Metyl

4,2 6,3

Vng

Clophenol

4,8 6,4

Vng

Bromtymol
xanh

6,0 7,6

Vng

Xanh bin

Phenol

6,4 8,0

Vng

trung tnh

6,8 8,0

Vng da cam

7,4 9,0

Vng

gch

1,2 2,8

Vng

Phenolphtalein

8,0 9,6

Khng mu

Tymolphtalein

9,3 10,5

Khng mu

Xanh bin

Alizarin vng

10,1 12,0

Khng mu

Tm

Crezol

1. Ch th axit

: HIn + H2O U H3O+ + In,

2. Ch th kim : In + H2O U InH + OH.

Phn ln nhng ch th axit - baz c cu to c trng c chia thnh 6 loi. Ba trong
s cc loi c cp ti di y.
Nhng ch th phtalein: Phn ln nhng ch th phtalein khng mu trong dung dch axit
v c mu trong mi trng kim. Trong mi trng kim mnh mu ca chng b mt chm.
Trong mt s trng hp iu l khng thun li. Thng nhng ch th phtalein tan va
phi trong nc. chun b dung dch ch th ngi ta thng dng etanol. C th biu din
phenolphtalein theo cng thc cu to nh sau:

7
OH

OH

OH

OH

+ 2H2O
C

+
C

O
C

H3O+

OH
C

O
O

Khng mu

Khng mu

OH

OH

+
C

OH
C

C
O
O

Khng mu

H3O+

O
O

y l ch th ph bin nht trong s nhng ch th phtalein.

Chng ta nhn thy rng, cn bng th hai dn ti s to thnh vng quinon v s c mt
ca vng ny trong phn t hp cht thng quyt nh mu ca n. Nng ng k ca ion
mu c quan st thy vng pH = 8,0 9,6; pH m quan st thy s xut hin mu
ph thuc vo nng ch th v vo s nhy cm ca th gic ngi quan st.
Nhng ch th phtalein khc, khc vi phenolphtalein l c trong vng phenol cc nhm
chc; v d trong phn t tymolphtalein hai nhm alkyl c gn vo mi vng. Nhng bin
i cu trc c bn gn lin vi s chuyn mu ca ch th , tng t nh m t i vi
phenolphtalein.
Nhng ch th sulfophtalein: c trng ca nhiu ch th sulfophtalein l c hai khong
chuyn mu; mt khong c quan st thy trong dung dch kh axit, mt khong khc trong
mi trng trung tnh hoc kim va phi. Khc vi cc cht mu phtalein, cc ch th loi ny
c dng kim mu rt bn trong mi trng kim mnh.
chun b cc dung dch ch th, ngi ta thng s dng mui natri ca sulfophtalein
bi v bn thn ch th c tnh axit r rt. C th iu ch dung dch trc tip t mui natri
hoc bng cch ha tan sulfophtalein trong mt th tch tng ng dung dch natri hiroxit
long trong nc.
Phenolsulfophtalein c bit di tn phenol l ch th n gin nht. Nhng cn
bng quan trng nht i vi ch th l nh sau:

8
OH

OH

OH

-1,5

H2O

Ka = 10

H3O+

H3O+

SO3

SO3

OH

Vng
O

O
+

H2O

Ka = 10-7,9

SO3

SO3

Vng

S qu gi thc t ch l khong chuyn mu th hai trong hai khong chuyn mu quan

st thy khong pH = 6,4 8,0.
Thay th cc nguyn t hiro vng phenol ca hp cht ban u bng cc halogen hoc
cc nhm alkyl s thu c nhng sunfophtalein khc nhau v mu sc v khong pH chuyn
mu.
Nhng ch th azo: Khi tng kim ca mi trng mu ca phn ln cc ch th azo
bin i t mu sang vng; im chuyn mu ca ch th chuyn dch mt cht v vng
axit. Metyl da cam v metyl l nhng i din ph bin nht ca loi ch th . C th m
t tnh cht ca metyl da cam nh sau:

O3S

O3S

H+
N N

H+
N(CH3)2
+ H2O
N(CH3)2

O3S

N(CH3)2 + H3O+

Vng

Metyl c c trng bng cng thc tng t cng thc ca metyl da cam, ch loi
tr nhm sunfo trong vng v thay th bng nhm cacboxyl. Thay th cc nhm th nit

ca nhm amino v trong vng s thu c hng lot ch th c tnh cht khc nhau mt
cht.

10.2.3 Sai s chun vi cc ch th axit - baz

Cn phn bit hai loi sai s chun . Sai s h thng do pH chuyn mu ca ch th
khc vi pH im tng ng ca phn ng ha hc dng chun l sai s loi th
nht. C th gim sai s n cc tiu bng cch la chn cn thn ch th. Th nghim trng
s cho b chnh tng ng.
Sai s ngu nhin do kh nng ca ngi quan st phn bit mt cch lp li thi im
chuyn mu b hn ch l loi sai s th hai. Gi tr ca sai s ph thuc vo s bin i
pH trn mt mililit thuc th im tng ng, nng ch th v phng php nh phn
tch dng phn bit hai mu ca ch th. Khi quan st bng mt vi ch th axit - baz sai s
trung bnh khong 0,5 n v pH. So snh mu ca dung dch b chun cha lng ch th
"i chng" gi tr pH tng ng thng cho php h thp sai s n 0,1 n v pH hoc
nh hn. R rng, l nhng gi tr gn ng v mc ng k chng ph thuc vo bn
cht ca ch th cng nh vo trnh ca ngi thc hin.

10.2.4 Nhng yu t nh hng ti tnh cht ca ch th

Nhit , lc ion, s c mt ca nhng dung mi hu c v cc ht keo nh hng n
gi tr khong pH chuyn mu ca mt s cht ch th nht nh. Mt s trong nhng yu t
, c bit l hai yu t cui cng c th lm chuyn dch khong i mu i mt hoc mt
s ln hn n v pH.

10.3 ng chun axit mnh hoc baz mnh

Nu c cht chun v cht b chun l axit mnh v baz mnh th c th hnh dung phn
ng axit - baz tng th bng phng trnh:
H3O+ + OH = 2H2O
v c th xy dng ng chun trong trng hp ny tng t nh lm trong
phng php chun kt ta.

10.4.1 Chun axit mnh bng baz mnh

Nhng ion hiro trong cc dung dch nc ca axit mnh xut pht t hai ngun:
1. Do tng tc ca axit tan vi nc;

10

2. Do s phn li ca chnh nc. Trong cc dung dch khng qu long phn

ng gp ca phn ng gia cht tan vi dung mi vo axit tng cng ln hn nhiu phn
ng gp do dung mi phn li. Do , i vi dung dch HCl c nng ln hn 1.106 M:
[H3O+] = CHCl

(10.1)

Nu nng dung dch thp hn 1.106 M, tnh [H3O+] c th s dng phng trnh
chnh xc hn, thu c t iu kin trung ha in tch:
[H3O+] = [Cl] + [OH] = CHCl +

K H2O

[H3O+ ]

(10.2)

Thnh phn u tin phn bn phi ca phng trnh l lng ion hiro to thnh do
HCl phn li, cn thnh phn th hai l lng ion hiro to thnh do nc phn li.
Nhng lp lun tng t cng ng n i vi dung dch baz mnh, v d i vi natri
hiroxit:
[OH] = CNaOH
R rng l i vi baz phn li hon ton, Ba(OH)2:
[OH] = 2 CBa(OH)2
C th thu c phng trnh thun tin tnh pH ca cc dung dch kim bng cch ly
logarit phng trnh biu thc tch s ion nc:
l o g K H2O = l o g([H3 O+ ][OH ]) = l o g[H3 O+ ] lo g[OH ]
pK H2O = pH + pOH

25oC, pK H2O = 14,00.

Nh s c ch r trong v d dn ra di y, vic xy dng ng chun axit mnh
bng baz mnh khng kh khn g bi v nng ion hiro hoc ion hiroxyl c tnh ton
trc tip t nng chung hoc axit d hoc baz d.
V d: Hy xy dng ng chun 50,00 ml dung dch HCl 0,050 M bng dung dch
NaOH 0,100 M. Nhng gi tr pH thu c c lm trn n s l th hai sau du phy.
Gi tr pH u: Chng ta c dung dch HCl 5.102 M. V HCl phn li hon ton:
[H3O+] = 5.102 mol/l,
pH = log(5,00.102 ) = log 5,00 lo g102

= 0,699 + 2 = 1,301 = 1,30

11

Gi tr pH sau khi thm 10,00 ml dung dch NaOH: Th tch dung dch tr thnh 60,00
ml v mt phn HCl c chun , do :
50,00 0,050 10,00 0,100
= 2,50.102 mol / l
60,00
pH = 2 l og 2,50 = 1,60

[H3 O+ ] =

Bng cch tng t, ngi ta tnh pH cho n tn im tng ng. Nhng kt qu tnh
ton c gii thiu trong ct 2 ca bng 10.2.
Gi tr pH sau khi thm 25,00 ml dung dch NaOH: thi im trong dung dch
khng cn d HCl v cng khng d NaOH v pH c xc nh bng s phn li ca nc:
[H3 O+ ] = [OH ] = K H2O = 1,00.10 7 mol / l;pH = 7

Gi tr pH sau khi thm 25,10 ml NaOH:

CNaOH =

25,10 0,100 50,00 0,0500

= 1,33.104 M
75,10

Gi thit rng nng OH to thnh do s phn li ca nc nh hn so vi CNaOH.

[OH] = 1,33.104 ion.g/l
pOH = 3,88
pH = 14,00 3,88 = 10,12
Trong ct th hai ca bng 10.2 dn ra nhng d kin b sung ca php chun trn,
c tnh ton tng t.
Bng 10.2 S bin i pH khi chun axit mnh bng baz mnh

pH
Th tch dung dch
NaOH, ml

Chun 25,0 ml
HCl 0,050 M bng
NaOH 0,100 M

Chun 25,0 ml HCl 0,0005 M

bng NaOH 0,0010 M

0,00

1,30

3,30

10,00

1,60

3,60

20,00

2,15

4,15

12

24,00

2,87

4,87

24,90

3,87

5,87

25,00

7,00

7,00

25,10

10,12

8,12

26,00

11,12

9,12

30,00

11,80

9,80

nh hng ca nng : Hai lot d kin c dn ra bng 10.2 phn nh nh hng

ca nng cht chun v cht b chun n dng ca ng chun axit - baz. S din t
bng th cc d kin c gii thiu trn hnh 10.1.

Hnh 10.1
Nhng ng chun HCl bng dung dch NaOH chun
1. Chun 25,0 ml HCl 0,0005 M bng NaOH 0,0010 M.
2. Chun 25,0 ml HCl 0,050 M bng NaOH 0,100 M.

Khi chun bng dung dch NaOH 0,100 M (ng cong 1) vng im tng ng,
quan st thy bc nhy pH ln, trong trng hp chun bng dung dch NaOH 0,001 M
bc nhy pH nh hn nhiu nhng rt cuc vn hon ton nhn thy c.
T hnh 10.1 r rng l nng cht chun 0,100 M, vic la chn ch th khng kh
khn. Trong trng hp hiu s th tch cht chun tiu tn cho php chun khi dng c ba
ch th c nu ln trn hnh v ch bng sai s c trn buret v do khng ng k. Mt

13

khc, bromcrezol lc r rng l khng thch hp cho php chun bng dung dch chun
0,001 N, khng ch v s chuyn mu ch th c quan st thy trong mt khong ln th tch
cht chun m cn v s chuyn ch th thnh dng kim thc t xy ra rt sm trc khi t
ti im tng ng v do xut hin sai s xc nh ln. Cng do chnh nguyn nhn
m ny sinh s bt ng v s s dng phenolphtalein. Trong s ba ch th xt ch c
bromtimol xanh cho php xc nh im cui vi sai s nh nht.

10.4.2 Chun baz mnh bng axit mnh

Tnh hnh tng t c quan st thy khi chun baz mnh bng axit mnh. gn im
tng ng, dung dch l kim mnh v nng ca ion hiroxyl bng nng ca kim
mnh cha c chun . Mt cch chnh xc, cng theo nhng nguyn nhn xt trn
y, dung dch im tng ng tr thnh trung ha. Cui cng, dung dch sau im
tng ng tr thnh axit v trng hp ny ngi ta tnh pH theo lng axit mnh d thm
vo. ng chun baz mnh bng HCl 0,100 M c gii thiu trn hnh 10.5. Ngi ta
chn ch th cng nh trng hp chun axit mnh bng baz mnh.

10.4 ng chun axit yu hoc baz yu

Khi xy dng ng chun axit yu cn phi tnh pH ca dung dch chnh axit lin
hp vi baz ca n v hn hp ca chng. Nhng tnh ton tng t cng cn thit khi xy
dng chun baz yu. Nhng phng php tnh pH ca dung dch axit yu v baz lin
hp c xem xt chng 4. Tnh pH ca cc dung dch cha mt lng ng k cp
axit - baz lin hp s c xem xt trong chng sau.

10.4.1 Tnh pH ca dung dch cha mt cp axit - baz lin hp

Dung dch cha mt cp axit - baz lin hp c th l axit, kim hoc trung tnh ty
thuc vo hai cn bng cnh tranh tn ti trong dung dch. i vi axit yu HA v mui natri
NaA ca n, nhng cn bng l:
HA + H2O U H3O+ + A ; K a =
A+ H2O U OH + HA

; Kb =

[H3 O+ ][A ]
[HA]

[OH ][HA]
[A ]

(10.3)

(10.4)

Nu cn bng th nht chuyn dch v bn phi mnh hn cn bng th hai th dung dch
s axit. Ngc li, nu cn bng th hai chim u th th dung dch s kim. T cc phng
trnh hng s cn bng y, r rng l nng tng i ca ion hiro v hiroxyl ph thuc
khng ch vo cc i lng Ka v Kb m cn ph thuc vo t s nng ca axit v baz
lin hp vi n.

14

Dung dch baz yu cng hon ton tng t. Trong dung dch cha amoniac
v amoni clorua, cc cn bng sau y c thit lp:
NH3 + H2O U NH4+ + OH,
Kb =

[NH4 + ][OH ]
= 1,76.105
[NH3 ]

NH4+ + H2O U NH3 + H3O+,

Ka =

[NH3 ][H3 O+ ]
[NH4+ ]

K H2O
Kb

1,00.1014
1,76.10

= 5,68.1010

V Kb ln hn Ka nhiu nn trong dung dch cn bng th nht chim u th v dung dch

s kim. Nhng nu nng NH4+ ln hn nng NH3 khong 200 ln, s khc nhau v gi
tr hng s cn bng c b tr v dung dch trong trng hp s axit.
Tnh pH ca dung dch cha axit yu v baz lin hp vi n: Chng ta xt dung dch c
nng axit chung CHA v nng baz lin hp chung CNaA. Nhng cn bng quan trng
nht v nhng h thc hng s cn bng y c m t bng cc phng trnh (10.3) v
(10.4).
Do kt qu ca phn ng (10.3), nng axit HA gim xung mt gi tr bng [H3O+]; mt
khc, do kt qu ca phn ng (10.4) nng axit HA tng mt gi tr bng [OH]. Nh vy, c
th din t nng cn bng ca axit HA bng phng trnh:
[HA] = CHA [H3O+] + [OH]

(10.5)

Mt cch tng t, do kt qu ca phn ng (10.3) [A] tng ln mt gi tr bng [H3O+],

trong khi do kt qu ca phn ng (10.4) [A] gim i mt gi tr bng [OH]:
[A] = CNaA + [H3O+] [OH]

(10.6)

Di y s ch r rng, phng trnh (10.5) c th d dng thu c t phng trnh cn

bng vt cht v iu kin trung ha in. Trong dung dch, [HA] v [A] c to thnh t hai
ngun HA v NaA m nng chung ca chng bit, do :
CHA + CNaA = [HA] + [A]

(10.7)

iu kin trung ha in i hi:

[Na+] + [H3O+] = [A] + [OH]
nhng v:
[Na+] = CNaA

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nn:
CNaA + [H3O+] = [A] + [OH]

(10.8)

Sau khi bin i phng trnh , chng ta i ti phng trnh (10.6):

[A] = CNaA + [H3O+] [OH]
Ly phng trnh (10.8) tr phng trnh (10.7) v bin i ta thu c:
[HA] = CNaA [H3O+] + [OH]
ngha l mt phng tnh tng t phng trnh (10.5).
Trong phn ln trng hp chng ta s ng chm ti vn l hiu s
([H3O+]

[OH ]) nh hn rt nhiu so vi c hai nng chung. Trong cc iu kin cc phng

trnh (10.5) v (10.6) c n gin ha:
[HA] CHA

(10.9)

[A] CNaA

(10.10)

Thay cc phng trnh thu c vo phng trnh hng s phn li, sau khi bin i ta
c:
[H3O+ ] = K a

CHA
CNaA

(10.11)

Trong cc ti liu v sinh vt v ha sinh thng gp mt s dng khc ca phng trnh

(10.11). Dng thu c khi din t mi thnh phn ca phng trnh di dng m logarit
v chuyn ch t s nng :
log[H3O+ ] = log K a lg

CHA
CNaA

T :
pH = pK a + lg

CNaA
CHA

(10.12)

Biu thc ny c tn l phng trnh Henderson-Schwazenbach.

Gi thit dn ti phng trnh (10.9) v (10.10) i khi khng c gi tr i vi axit hoc
baz c hng s phn li ln hn 103 hoc l trong trng hp nu nng chung ca axit
hoc baz lin hp ca n (hoc c hai cu t ca cp axit - baz lin hp) rt nh. Nh trong
cc tnh ton trc y, sau khi thc hin cc gi thit tng ng, nhng gi tr [H3O+] v

16

[OH ] tm c trong cc tnh ton s b, cn c s dng kim tra ng n

ca nhng gi thit (1) .
T phng trnh (10.11) ta thy rng, trong dung dch cha axit yu v baz lin hp vi
n, nng ion hiro ch ph thuc vo t s nng chung ca cc cht ny; iu ng
trong khong nng tha mn nhng gi thit, t rt ra phng trnh (10.11) cn c
ngha. Ngoi ra, gi tr h thc khng ph thuc vo s pha long dung dch, bi v khi
bin i th tch dung dch, nng ca mi cu t bin i mt s ln nh nhau. Nh vy,
nng ion hiro trong dung dch cha mt lng ng k axit yu v baz lin hp vi n,
khng ph thuc vo pha long v c xc nh ch bng t s nng chung ca c hai
cht tan. S khng ph thuc ca pH vo long l mt trong nhng biu hin tnh cht
m ca nhng dung dch .
V d: pH ca dung dch cha 0,400 M axit focmic v 1,00 M natri focmiat bng bao
nhiu ?
Nng ca ion hiro trong dung dch c xc nh bng cn bng ca phn ng:
H2O + HCOOH U H3O+ + HCOO
hng s cn bng ca cn bng l:
Ka =

[H3 O+ ][HCOO ]
= 1,77.104
[HCOOH]

Theo iu kin bi tp:

[HCOO] C HCOO = 1,00 M
[HCOOH] CHCOOH = 0,400 M
v:
[H3 O+ ] 1,00
= 1,77.10 4
0,400

t :
[H3O+] = 7,08.105 mol/l
pH = log(7,08.105) = 4,150 = 4,15
(1)

Nu [H3O+] c gi tr ln, dung dch s axit v c th b qua gi tr [OH]. Ngc li nu

dung dch l kim s c [OH] l ch yu v c th khng cn k ti gi tr [H3O+].

17

Nu chng ta so snh pH ca dung dch vi pH ca dung dch axit focmic 0,400 M th

thy rng, khi thm natri focmiat, nh hng ca ion cng tn dn ti s tng pH t 2,08 n
4,15.
Tnh pH ca dung dch baz yu v axit lin hp vi n: Tnh pH ca mt dung dch cha
baz yu v axit lin hp vi n khng c g khc vi v d phn tch trn.
V d: Tnh pH ca dung dch cha NH4Cl 0,28 M v NH3 0,070 M.
Cn bng chng ta ch l:
NH3 + H2O U NH4+ + OH
c c trng bng hng s Kb =1,76.105.
Nh thng l, chng ta c th gi thit rng :
[NH3] CNH3 = 0,070
[NH4+ ] CNH+ = 0, 28
4

Thay th nhng gi tr vo phng trnh hng s cn bng chng ta c:

[OH ] 0,28
= 1,76.105
0,070

[OH] = 4,40.106 mol/l

pOH = log(4,40.106) = 5,36;
pH = 14 5,36 = 8,64.

10.4.2 nh hng ca lc ion n cn bng axit - baz

Trong chng 4 ch r mc phn li ca axit yu, v d axit axetic tng ln cng vi
s tng ca lc ion. Nguyn nhn ca hin tng tng t nguyn nhn gy nn s chuyn
dch cn bng kt ta-dung dch. V dng khng phn li ca axit khng tch in nn s bin
i lc ion t nh hng n tnh cht ca n; mt khc, v s bin i lc ion nh hng n
tnh cht cc ion ca cht in li, khuynh hng cc ion hiro v ion axetat ti lin hp b
gim xung.
V d dn ra di y ch r rng c th tnh ton nh hng ca lc ion nu bit h s
hat ca cc ion.

18

V d: Tnh pH ca dung dch m cha 0,0400 M axit focmic v 0,100 M natri

focmiat, theo hot . So snh kt qu thu c vi kt qu tm c khi s dng nng
thay th cho hot .
Gi thit mt cch hp l rng, lc ion ca dung dch c xc nh bng nng
natri focmiat, ngha l nng H3O+ v ion focmiat to thnh khi axit focmic phn li nh:
=

1
(0,100.12 + 1,00.12) = 0,100.
2

T bng 5.4 (xem chng 5) chng ta tm thy rng i vi = 0,1:

fH

+
3O

= 0,83;

fHCOO = 0,76

Nh vy:
Ka =

[H3 O+ ][HCOO ] fH3O+ fHCOO

= 1,77.104
[HCOOH]
fHCOOH

Hp nht h s hot i vi Ka chng ta tnh c hng s nng ca cn bng K 'a :

K a' =

1,77.104 fHCOOH 1,77.104 1,0

[H O+ ][HCOO ]
=
= 2,81.104 = 3
fH O+ fHCOO
0,83 0,76
[HCOOH]
3

Chng ta nhn thy rng h s hot ca HCOOH khng tch in c chp nhn
bng 1,0. Gi thit i vi ht trung ha thng l ng.
Sau ny, tnh ton chng ta s dng hng s cn bng nng Ka':
[HCOO] = 0,100 M
[HCOOH] = 0,0400 M
[H3 O+ ] 0,100
= 2,81.104
0,0400

[H3O+] = 1,12.104 mol/l;

pH = log(1,12.104) = 3,95.
Ch rng, nu khng tnh h s hot chng ta thu c pH = 4,15.

19

10.4.3 Dung dch m

Dung dch m l dung dch c pH khng bin i trong cc trng hp:
1. Khi pha long;
2. Khi thm vo mt lng nh axit hoc baz. Dung dch c nng axit v baz lin
hp vi n cao v xp x bng nhau l tt nht.
nh hng ca s pha long: Gi tr pH ca dung dch m thc t khng bin i khi
pha long cho ti khi nng ca n khng gim ti mc l, s gn ng c s dng
rt ra phng trnh (10.9) v (10.10), tr thnh mt gi tr. V d dn ra di y minh ha
tnh cht in hnh ca dung dch m khi pha long.
V d: Hy tnh pH ca dung dch m c pH = 4,15 khi pha long dung dch m (xem
v d mc 10.4.1):
1. 50 ln;
2. 10.000 ln.
Gii:
1. Sau khi pha long 50 ln:
CHCOOH = 0,400/50 = 8,00.103 M
CHCOONa = 1,00/50 = 2,00.102 M
Nh trc y, nu gi thit rng, hiu s [H3O+] [OH] nh so vi CHCOOH v CHCOONa
ta c:
[H3O+ ] 2,00.102
8,00.103

= 1,77.104

[H3O+] = 7,08.105 mol/l; pH = 4,15.

Trong trng hp :
[OH ] =

1,00.10 14
7,08.10

= 1,41.1010 mol / l

Nh vy gi thit (7,08.105 1,41,1010) << 8,00.103 v 2,00.102 c c s.

2. Sau khi pha long 10.000 ln:

20
5

CHCOOH = 4,00.10 M
CHCOONa = 1,00.104 M
Trong trng hp ny cn s dng phng trnh (10.5) v (10.6), chng cho nhng kt
qu chnh xc hn:
[HCOOH] = 4,00.105 [H3O+] + [OH]
[HCOO] = 1,00.104 + [H3O+] [OH]
V dung dch l axit nn chc chn phi c [H3O+] >> [OH], nh vy:
[HCOOH] 4,00.105 [H3O+];
[HCOO] 1,00.104 + [H3O+]
Thay th cc gi tr vo phng trnh hng s cn bng ta c:
[H3 O+ ] (1,00.1014 + [H3O+ ])
4,00.105 [H3O+ ]

= 1,77.104

a phng trnh n dng bc hai:

[H3 O+ ]2 + 2,77.10 4 [H3O+ ] 7,08.10 9 = 0

v gii ra:
[H3O+] = 2,36.105 mol/l; pH = 4,63.
Nh vy, khi pha long 10.000 ln pH tng t 4,15 n 4,63 v khi pha long 50 ln pH
thc t khng bin i.
Trn hnh 10.2 dn ra s so snh nh hng ca s pha long n pH ca cc dung dch
m v khng m vi nng u ca mi dung dch bng 1,00 M. T hnh v thy r rng
l nhng dung dch m t bin i pH.
Thm axit v baz vo dung dch m: Kh nng ca dung dch m gi khng i gi tr
pH khi thm axit hoc baz vo c chng ta minh ha v d sau.
V d: Hy tnh xem pH bin i nh th no nu thm vo 400 ml dung dch m cha
NH3 0,200 M v NH4Cl 0,300 M.
1. 100 ml NaOH 0,0500 M;

2. 100 ml HCl 0,500 M.

Chng ta tnh gi tr pH ban u, khi gi thit rng:

21

[NH3] CNH3 = 0,200 M

[NH4+ ] CNH4Cl = 0,300 M

v thay th nhng gi tr vo phng trnh hng s phn li:

[OH ] 0,300
= 1,76.105
0,200

[OH] = 1,17.105 mol/l; pH = 14,00 (log1,17.105) = 9,07

Hnh 10.2
nh hng ca s pha long n pH ca cc dung dch m v khng m.

Hng s phn li HA bng 1,00.104. Nng u i vi tt c cc trng hp bng 1,00

M.
1. Thm NaOH vo gy nn s chuyn dch mt phn NH4+ thnh NH3:
NH4+ + OH

NH3 + H2O

Nng chung ca NH3 v NH4Cl sau khi thm kim vo tr thnh nh sau:

22
CNH3 =

400 0,200 + 100 0,0500

= 0,170 M
500

CNH4Cl =

400 0,300 100 0,0500

= 0,230 M
500

Sau khi thay th nng tm c vo phng trnh hng s phn li ca NH3 ta thu
c:
[OH ] =

1,76.105 0,170
= 1,30.105 mol / l
0,230

pH = 14 (log1,30.105) = 9,11
pH = 9,11 9,07 = 0,04
2. Thm HCl gy nn s chuyn mt phn NH3 thnh NH4+ , do :
CNH3 =

400 0,200 100 0,0500

= 0,150 M
500

CNH4Cl =

[OH ] =

400 0,300 + 100 0,0500

= 0,250 M
500

1,76.105 0,150
= 1,06.105 mol / l
0,250

pH = 14 (log1,06.105) = 9,02
pH = 9,02 9,07 = 0,05
V d: Hy so snh tnh cht ca dung dch khng m c pH = 9,07([OH] = 1,17.105
mol/l), khi thm vo cng mt lng kim v axit nh trong v d trn.
1. Sau khi thm kim:
[OH ] =

400 1,17.105 + 100 0,0500

= 1,00.102 mol / l
500

pH = 14 (log1,00.102) = 12,00
pH = 12,00 9,07 = 2,93
2. Sau khi thm axit clohiric:
[H3 O+ ] =

100 0,05 400 1,17.10 5

= 1,00.10 2 mol / l
500

23

pH = log(1,00.102) = 2,00
pH = 2 9,07 = 7,07
Khi lng m: nhng v d xt ch r rng dung dch cha cp axit - baz lin hp
c kh nng gi pH n nh khi pH ca dung dch b bin i. Tnh cht gi pH n nh ca
dung dch m i vi s bin i ng k ca pH ph thuc c vo nng chung ca cc
cu t ca dung dch m c vo t s ca chng. V d, nu thm vo 400 ml dung dch m
thu c bng cch pha long 10 ln dung dch m m t trong v d trn, cng mt
lng nh th natri hiroxit hoc axit clohiric th pH ca n bin i khong 0,5 n v;
i vi dung dch m c hn, s bin i pH ch khong 0,04 n v.
Ngi ta o khi lng m ca dung dch bng s mol axit mnh hoc baz mnh cn
thit phi thm vo mt lt dung dch m lm bin i pH ca n mt n v. Chng ta
cng thy rng, khi lng m ph thuc vo nng cp axit - baz lin hp ng thi
c vo t s nng ca cp axit - baz lin hp v t ti gi tr cc i khi t s bng
n v.
Chng ta xt dung dch m cha a mol axit HA v b mol baz lin hp NaA. Nu thm
vo dung dch n mol axit mnh, nng chung ca axit v baz lin hp s nh sau:
a+n
;
v
bn
=
v

CHA =
CNaA

y v l th tch dung dch. Chng ta xc nh pH ca dung dch theo phng trnh

(10.12):
pH = pK a + log

CNaA
bn
= pK a + log
= pK a + log(b n) log(a + n)
CHA
a+n

Ly vi phn phng trnh theo n ta c phng trnh m t tc bin i pH ca dung

dch m khi thm axit:
dpH
1
1
= 0,434
0,434
dn
bn
a+n

Cho vi phn bc hai bng khng chng ta tm c cc tiu ca hm pH = F(n).

d2pH
dn

Sau khi bin i ta c:

= 0,434

1
2

(b n)

0,434

1
(a + n)2

=0

24

1
2

(b n)

1
(a + n)2

Khai cn bc hai c hai phn ca phng trnh v sp xp li ta c: b = a.

Nh vy, tc bin i pH cc tiu khi thm axit c quan st thy trong trng hp
nu s mol baz lin hp b bng s mol axit lin hp a. Ta cng c c mi quan h nh
vy nu thm baz vo dung dch m c iu ch t baz yu v axit lin hp vi n.
Gii hn ng dng phng trnh Henderson-Schwazenbach.
Phng trnh Henderson-Schwazenbach:
pH = pK a + log

CNaA
CHA

(10.12)

c s dng rng ri tnh pH v iu ch dung dch m. Trong phng trnh trn

pKa l hng s nn t s

CNaA
quyt nh gi tr pH ca dung dch, nhng trong thc t, iu
CHA

ch ng trong mt khong xc nh. Khi t s ny rt ln hoc rt nh, phng trnh trn

tr thnh khng ng v khng th p dng c. V d, khi

CNaA 1.101
=
= 1.106 th i

7
CHA
1.10

vi h NaCH3COO - CH3COOH, pH ca dung dch s l:

pH = 4,76 + log106 = 4,76 + 6,00 = 10,76
Kt qu trn l khng th chp nhn c v ln hn nhiu pH ca dung dch
NaCH3COOH 0,100 M, ng thi cng chnh l pH im rt gn vi im tng ng
trong php chun dung dch CH3COOH 0,200 M bng dung dch NaOH 0,200 M (xem mc
10.4.4 di y). V lc ny [NaCH3COO] >> [CH3COOH] nn:
[OH ] = K bCb =

K H2O
Ka

CNaCH3COO =

10 14
10

4,76

10 1 = 1.105,12

pOH = 5,12
do
pH = 14,00 5,12 = 8,88
Ngc li, khi

CNaA 10 7
=
= 106 th i vi h NaCH3COO - CH3COOH ta ang xt
1
CHA
10

pH s l:
pH = 4,76 + log106 = 4,76 6,00 = 1,24

25

Kt qu ny cng khng th chp nhn c v dung dch ny thc t l dung dch

CH3COOH 0,100 M, ng thi pH ca n cng chnh l pH im u, chnh xc hn l
im "cc k st" vi im u ca ng chun dung dch CH3COOH 0,100 M bng
dung dch NaOH 0,100 M (v [CH3COOH >> [NaCH3COO]) nn:
[H3 O+ ] = K CH3COOH CCH3COOH = 104,76 101 = 102,88 (xem 10.4.4)

pH = 2,88.
Khi sinh vin mun tnh pH im "v cng st" vi im u v im "v cng st" vi
im tng ng ca php chun axit yu bng baz mnh nhng li bng phng trnh
phng trnh Henderson-Schwazenbach th phm phi nhng sai lm nh trn.
S tht l h m axit yu v baz lin hp vi n c khi lng m (xem khi lng
m 10.4.3) cc i khi CHA = CNaA v khi lng m gim dn v c hai pha khi CHA v
CNaA gim dn. Khi CHA = 107 ngha l CHA 0 v CNaA = 107 ngha l CNaA 0 l lc
khi lng m ca h tin ti khng nn h khng cn l h m na v do khng th
dng cng thc ca Henderson-Schwazenbach tnh pH.
iu ch dung dch m: V nguyn tc c th iu ch dung dch m c pH cn thit
bt k bng cch trn nhng lng c tnh ton trc ca nhng cp axit - baz lin hp
thch hp.
V d: Hy trnh by cch iu ch dung dch m c pH = 5,00 t dung dch axit axetic
(Ka = 1,75.105) 0,500 M v dung dch NaOH 0,426 M.
Ta tm c t s nng axit axetic v anion axetat pH = 5,00 t phng trnh hng
s phn li:
[OAx ] K HOAx 1,75.105
=
=
= 1,75
[HOAx] [H3O+ ] 1,00.105

c c t s cn trn VHA ml axit axetic vi VOH ml NaOH 0,426 M. Sau khi trn,
nng axit v baz lin hp s tng ng bng:
COAx =
CHOAx =

0,426 VOH
VHA + VOH

[OAx ]

0,500 VHA 0,426 VOH

VHA + VOH

[HOAx]

Nu thay th [OAx] v [HOAx] bng nhng nng vo t s ban u th mu s

c n gin ha:

26
0,426 VOH
0,500 VHA 0,426 VOH

= 1,75

v sau khi sp xp li chng ta thu c:

VOH
VHA

= 0,747

Nu cn thit iu ch 100 ml dung dch m th chng ta lm nh sau:

VOH + VHA = 100
0,747VHA + VHA = 100
VHA = 57,2 ml; VOH = 100 57,2 = 42,8 ml
Nh vy, nu thm 57,2 ml dung dch axit axetic vo 42,8 ml dung dch NaOH th v
nguyn tc phi thu c dung dch c pH cn thit. Bng cc tnh ton loi tng t c th
hng dn vic iu ch cc dung dch m c pH xp x pH tng ng cn thit. Thng
khng nn mong i cc gi tr chnh xc bi v gi tr ca nhiu hng s phn li c sai s.
Cn mt iu quan trng hn na l lc ion ca cc dung dch m thng ln dn n mc
l khng th thu c gi tr h s hot tin cy ca cc ion trong cc dung dch t
phng trnh Debye-Huckel. Nh trong v d xt, lc ion khong 0,18 v vy hng s phn
li nng K 'a cn phi ln hn 1,75.105 ng k nhng cha c xc nh chnh xc
(khong 3.105).
Nhng hng dn iu ch cc dung dch m c pH bit trc c trong cc s tay tra
cu ha hc. Cn c bit nh hai h m ph bin nht: dung dch m Makilvein i vi
khong pH = 2 8 c iu ch bng cch trn dung dch axit xitric v natri hiro-photphat
v dung dch m Klark v Labo i vi khong pH = 2 10 c iu ch bng cch s
dng ba h: axit phtalic-kali biphtalat, kali ihiro photphat-kali hiro photphat, axit boric v
natri borat.

10.4.4 ng chun axit yu

xy dng ng chun axit yu (hoc baz yu) cn phi thc hin bn loi php
tnh tng ng vi bn phn ca ng cong:
1. Trc khi chun, dung dch ch cha axit yu, nn pH ca dung dch c tnh theo
nng cht b chun.
2. Sau khi thm mt phn bt k thuc th (mt lng cho ti trc im tng ng
nhng cha bng lng tng ng), cc dung dch s l mt lot h m; i vi mi h
m c th tnh pH theo nng chung ca sn phm phn ng v ca axit hoc baz
cha b chun.

27

3. im tng ng dung dch cha hp cht lin hp vi axit yu hoc baz yu b

chun v pH c tnh theo nng chung ca hp cht .
4. Cui cng, sau im tng ng lng d axit mnh hoc baz mnh c dng lm
cht chun ti mc ngn cn phn ng ca sn phm to thnh nn pH ch yu c xc nh
theo nng lng d cht chun.
Xy dng ng chun : Chng ta xt nhng tnh ton v d xy dng ng
chun 50,00 ml dung dch axit axetic (Ka = 1,75.105) 0,100 M bng dung dch NaOH
0,100 M.
Gi tr pH ban u: S dng phng php m t trc y chng 4 cho dung dch
HOAx 0,100 M chng ta c pH = 2,88.
Gi tr pH sau khi thm 10,00 ml cht chun: Trong trng hp ny chng ta thu c
dung dch m gm c NaOAx v HOAx. Ta phi tm nng ca c hai cu t ca dung
dch m:
5 0, 0 0 0,1 0 0 0 1 0, 0 0 0 0,1 0 0 0
4, 0 0 0
=
6 0, 0 0
6 0, 0 0
1 0, 0 0 0,1 0 0 0 1, 0 0 0
C N aO A x =
=
6 0, 0 0
6 0, 0 0

CH O Ax =

Thay th nhng gi tr tm c vo phng trnh hng s phn li HOAx chng ta thu

c:
[H 3 O + ] 1, 0 00
6 0, 0 0
= K a = 1,7 5.10 5
4, 00 0
6 0, 0 0

[H3O+] = 7,00.105 mol/l pH = 4,16

Bng 10.3 S bin i pH khi chun axit yu bng baz mnh

pH
Th tch dung dch
NaOH ml

Chun 50,00 ml CH3COOH

0,100 M bng dung dch
NaOH 0,100 M

Chun 50,00 ml CH3COOH

0,00100 M bng dung dch
NaOH 0,00100 M

0,00

2,88

3,91

10,00

4,16

4,30

25,00

4,76

4,80

28

40,00

5,36

5,38

49,00

6,45

6,45

49,90

7,46

7,46

50,00

8,73

7,73

50,10

10,00

8,00

51,00

11,00

9,00

60,00

1196

9,96

75,00

12,30

10,30

Nhng tnh ton loi tng t, thch hp xy dng ng chun sut c vng
m. Nhng kt qu ca nhng tnh ton c gii thiu ct th hai ca bng 10.3. Ch
l nu axit b chun 50% (i vi php chun cho, iu tng ng vi s thm vo
chnh xc 25 ml dung dch kim) nng chung ca axit v baz lin hp bng nhau; trong
gii hn ca nhng gi thit thng thng, ngi ta cng nhn nng cn bng bng nhau
ca chng. Do trong phng trnh hng s phn li nhng i lng c n gin
ha v nng ion hiro bng tr s hng s phn li, ngha l pH bng pKa. Bng cch tng
t khi chun baz yu, nng ion hiroxyl thi im 50% baz c chun bng tr s
hng s phn li baz.
Gi tr pH im tng ng: im tng ng, axit axetic chuyn thnh natri
axetat ngha l chng ta c dung dch ch cha baz . Sau khi tnh nng tng qut ca
ion axetat ngi ta tnh pH nh m t i vi baz yu (chng 4). Trong v d cho,
nng baz NaOAx l 0,0500 M, do :
[OH ]

K H2O
Ka

0,0500 =

1,00 1014 0,0500

1,75.105

[OH ] = 5,34.10 6 mol / l

pH = 14,00 ( log 5,34.10 6 ) = 8,73

Gi tr pH sau khi thm 50,10 ml baz mnh: Sau khi thm 50,10 ml kim, ion hiroxyl
c to thnh do s phn li ca baz d v do tng tc ca ion axetat vi nc. S ng
gp ca phn ng sau qu nh bi v lng d baz mnh cn tr s phn li baz yu v c
th khng cn k ti n. iu tr thnh r rng khi chng ta tnh c nng ion
hiroxyl im tng ng trong php chun cho l 5,34.106 mol/l. S ng gp
[H3O+] do phn ng phn li ca axit axetic khi va xut hin lng d baz mnh s cn b
hn do :

29
[OH ] CNaOH =

50,10 0,1000 50,00 0,1000

= 1,0.104 mol / l
100,1

pH = 14,00 ( log1,0.10 4 ) = 10,00

Chng ta nhn thy rng ng chun axit yu bng baz mnh sau im tng
ng ging vi ng chun axit mnh bng baz mnh.
nh hng ca nng : Trong cc ct th hai v th ba ca bng 10.3 dn ra nhng d
kin thu c khi chun cc dung dch axit axetic 0,100 M v 0,001 M bng dung dch
NaOH c cng nng . V d dn ra di y ch r rng khi xy dng ng chun cc
dung dch long cn tnh ton nng ion hiro bng nhng phng trnh chnh xc hn.
V d: Hy tnh pH ca dung dch to thnh khi trn 50,00 ml dung dch axit axetic 0,001
M vi 10,00 ml dung dch NaOH 0,001 M.
Chng ta tnh nng HOAx v NaOAx:
50,00 0,001 10,00 0,001
= 6,67.10 4 M
60,00
10,00 0,001
=
= 1,67.10 4 M
60,00

CHOAx =
CNaOAx

Nu chng ta tnh [H3O+] bng chnh nhng phng trnh c s dng trong trng
hp chun bng cc dung dch thuc th 0,100 M th tm thy: [H3O+] = 7,00.105 mol/l. R
rng l gi tr [H3O+] tm c by gi c th snh vi CHOAx v CNaOAx do cn ng dng
cc phng trnh (9.5) v (9.6):
[HOAx] = CHA [H3O+] + [OH]
[OAx] = CNaA + [H3O+] [OH]
C th b qua gi tr [OH] bi v dung dch l axit. Thay th cc gi tr tm c vo
phng trnh hng s phn li ta c:
Ka =

[H3 O+ ] CNaA + [H3 O+ ]

(CHA [H3O+ ])

v sau khi chuyn thnh phng trnh bc hai:

[H3O+]2 + (CNaA + Ka).[H3O+] Ka.CHA = 0
i vi v d cho:
[H3O+]2 + 1,84.104.[H3O+] 1,17,108 = 0;

30
+

[H3O ] = 5,00.10 mol/l;

pH = 4,30
Gi tr pH i vi nhng thi im chun tng ng vi s thm vo t 10,00 n 49,00
ml dung dch baz mnh (bng 10.3, ct 3) c tnh ton tng t.
S din t bng th nhng d kin ca bng 10.3 c gii thiu trn hnh 10.3.
Chng ta nhn thy rng i vi dung dch long hn, gi tr pH ban u cao hn v pH
im tng thp hn so vi trng hp dung dch 0,100 M. cc im tng ng vi s
thm vo mt th tch trung gian cht chun, pH bin i t hn. Trong vng ca php
chun, dung dch m cha axit axetic v natri axetat c to thnh. Hnh 10.3 khng nh
li rng, s pha long t nh hng n pH ca dung dch m.
Trn hnh 10.4 dn ra nhng ng chun cc dung dch axit 0,100 M c cng
khc nhau. R rng l khi lm gim cng axit, s bin i pH trong vng im tng
ng tr nn t r rng hn bi v phn ng gia axit v baz xy ra km hon ton hn.
nh hng ca nng thuc th n hon ton ca phn ng (hnh 10.3) tng t
nh c m t trc y i vi ng chun kt ta (chng 9).

Hnh 10.3

Hnh 10.4

Nhng ng chun axit axetic bng dung dch

NaOH

nh hng ca cng axit n c im ca ng

chun .

1. Chun axit 0,100 M bng NaOH 0,100 M.

Mi ng cong tng ng vi php chun 50,00 ml axit

0,1000 M bng NaOH 0,1000 M

2. Chun axit 0,00100 M bng NaOH 0,00100 M

31

La chn ch th: Hnh 10.3 v 10.4 ch r rng, s la chn ch th cho php chun axit
yu b hn ch hn so vi php chun axit mnh. V d, brom crezol lc hon ton khng
thch hp cho php chun axit axetic 0,100 M; c brom timol chm cng t thch hp i vi
php chun axit axetic 0,100 M bi v s bin i mu ca n c quan st thy trong
khong t 47 n 50 ml baz mnh 0,100 M. Nhng c th dng brom timol chm nu chun
n mu hon ton kim; bin php i hi phi dng dung dch kim chun cha cng
mt lng ch th v dung dch b chun (i chng) so snh. chun , nhng ch th
c s chuyn mu trong mi trng kim nh phenolphtalein thch hp hn.
S bin i pH im cui khi chun axit axetic 0,00100 M (ng cong 2 trn hnh
10.3) nh n mc l c th gy sai s chun ln. xc nh im cui vi lp li mt
vi phn trm cn s dng ch th vi s chuyn mu trong vng chuyn mu t
phenolphtalein n brom timol chm v ngoi ra cn dng i chng.
T hnh 10.4 r rng l, nhng vn tng t ny sinh theo mc gim cng axit.
Khi chun axit 0,100 M vi hng s phn li 108 c th thu c chnh xc 2% iu
kin c i chng thch hp. C th chun nhng dung dch c hn ca nhng axit tng i
yu vi chnh xc kh.
Sau y xin dn ra mt v d v cch tnh bc nhy pH khi chun 20,00 ml dung dch axit
0,100 M c K a = 1.10 8 bng dung dch NaOH 0,100 M lm minh chng.
u bc nhy l lc php chun ang cn thiu 0,10 ml NaOH 0,100 M, ngha l
mt dung dch m nn pH = pK a log

0,1
= 8,00 + 2,30 = 10,30.
19,9

Ti im tng ng php chun thm 20,00 ml NaOH 0,100 M, h tr

thnh dung dch baz lin hp ca HA l NaA c V= 40,00 ml nn [NaA] = 5.102 M,
K b = 1.10 6 , OH = 1.10 6.5.102 = 2,24.104 M , pOH = 3,65, pH = 10,35.

Cui bc nhy l lc php chun tha 0,10 ml NaOH 0,100 M nn [OH] do

NaOH d to ra l:
O H - = 0,100 0,10

40,10
+
O H

1.10 6 .5.10 2 = 2, 24.10 4 M

O H
pOH = 0,68 + 4,00 = 3,32
pH = 10,68

= 2,50.10 4 M v O H do A to ra l

= 4,74.10 4 M

32

Vy bc nhy c pH = 0,38.
Vi bc nhy nh trn, kt hp vi khong chuyn mu ca ch th v iu kin c i
chng c th t chnh xc 2% nu trn l hp l.

10.4.5 ng chun baz yu

Xy dng ng chun baz yu khng c g khc vi xy dng ng chun axit
yu.
V d: Chun 50,00 ml dung dch NaCN 0,050 M bng dung dch HCl 0,100 M. Hy tnh
pH sau khi thm:
1. 00,00 ml;

2. 10,00 ml;

3. 25,00 ml;

4. 26,00 ml axit.

1. Thm 0,00 ml dung dch chun. Ion xianua l baz yu; tnh pH c tin hnh nh
ch ra chng 4.
[OH ] K b CNaCN

y:

Kb =

KH2O
KHCN

1,00.1014
2,1.10

= 4,76.106

Gi tr pH tm c l 10,69.
2. Thm 10,00 ml dung dch chun: s thm axit dn ti s to thnh dung dch m
cha:
50,00 0,050 10,00 0,100 1,500
=
60,00
60,00
10,00 0,100
1,00
=
=
60,00
60,00

CNaCN =
CHCN

Thay th cc gi tr vo phng trnh hng s phn li ca HCN ta c:

2,1.109 1,00
60,00
[H3 O+ ] =
= 1,4.109 mol / l
1,500
60,00

pH = 8,85.
3. Thm 25,00 ml dung dch chun: thm vo mt th tch nh vy cht chun cho php
t ti im tng ng; by gi trong dung dch c axit yu HCN:

33

CHCN =

25,00 0,100
= 0,03333 M v do (xem chng 4)
75,00
[OH ] K b CNaCN
= 2,1.109 0,03333 = 8,37.106 mol / l
pH = 5,08

4. Thm vo 26,00 ml cht chun: lng d axit mnh ngn cn s phn li HCN n mc
l s ng gp ca n vo gi tr pH khng ng k v do :
[H3 O+ ] = CHCl =

26,00 0,100 50,00 0,050

= 1,32.103 mol / l
76,00

pH = 2,88

Trn hnh 10.5 dn ra nhng ng chun baz yu c cng baz khc nhau. R
rng l khi chun baz yu c th s dng nhng ch th vi s chuyn mu trong vng axit.

Hnh 10.5
nh hng ca cng baz n dng ca ng chun .
Mi ng cong tng ng vi php chun 50,00 ml dung dch baz 0,1000 M bng HCl 0,1000 M