1

Chng 8. M u v phn tch th tch

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, Phn tch th tch, Phn ng, thuc th, Cht chun
gc, Dung dch chun, Phng php chun .

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 8 M u v phn tch th tch ....................................................................... 2
8.1

Nhng khi nim c bn........................................................................................ 2

8.2

Phn ng v thuc th dng trong phn tch chun ......................................... 3

8.2.1 Nhng cht chun gc....................................................................................... 3

8.2.2 Dung dch chun................................................................................................ 4
8.3

im cui trong cc phng php chun ......................................................... 4

Chng 8
M u v phn tch th tch

Trong nhiu trng hp, gii quyt nhim v phn tch, phng php phn tch trng
lng l phng php tt nht. Tuy vy, thi gian thc hin php phn tch trng lng
thng qu di nn nhiu khi khng p ng nhu cu ca sn xut cng nghip. l l do ra
i ca phng php phn tch th tch.
Phng php nh lng da trn php o th tch c gi l phng php phn tch th
tch hay phng php chun . Phng php chun c s dng rng ri hn phng
php trng lng v phng php ny nhanh hn, thun tin hn m nhy li khng thua
km.

8.1 Nhng khi nim c bn

Chun l qu trnh nh lng cht cn phn tch theo lng thuc th tiu chun tiu
tn. Php chun c thc hin bng cch thm mt cch thn trng dung dch thuc th
bit nng vo dung dch cht cn xc nh cho ti khi phn ng gia chng kt thc,
sau o th tch dung dch thuc th chun. i khi, nu iu khng thun tin hoc cn
thit, ngi ta thm d thuc th v sau chun ngc bng mt thuc th khc bit
nng xc nh lng d thuc th th nht khng tham gia phn ng.
Dung dch thuc th c nng chnh xc bit dng chun c gi l dung
dch chun. chnh xc ca nng dung dch chun hn ch chnh xc chung ca
phng php, do cn c bit ch vic iu ch cc dung dch chun. Nng dung dch
chun c xc nh hoc trc tip hoc gin tip:
1. Trc tip bng cch ho tan hon ton mt lng cn chnh xc thuc th chun gc v
pha long n th tch chnh xc bit bng nc ct.
2. Chun dung dch cha mt lng cn xc nh ca mt hp cht tinh khit bng
dung dch thuc th chun l cch gin tip.

Hp cht ha hc c dng lm cht chun phi c tinh khit cao c gi l cht

chun gc. Qu trnh xc nh nng dung dch chun theo cch chun bng dung dch
cht chun gc c gi l php chun ha.
Mc ch ca mt php chun bt k no cng l tm lng dung dch chun tng
ng v mt ha hc vi lng cht phn ng vi n (cht cn xc nh). iu t c
im tng ng. V d, trong php chun dung dch natri clorua bng dung dch bc
nitrat, im tng ng t c khi mt mol bc nitrat c thm vo mt mol natri clorua
trong mu. Khi chun axit sunfuric bng natri hiroxit im tng ng l lc thm hai
phn t gam kim vo mt phn t gam axit.
im tng ng l mt khi nim l thuyt. xc nh v tr thc t ca n, phi
quan st s bin i tnh cht vt l lin quan vi im tng ng. Nhng bin i ch
tr thnh r rng im cui ca php chun. Thng ngi ta cho rng hiu s th tch
im tng ng v im cui nh nhng lun tn ti do s khng tng ng gia qu
trnh bin i tnh cht vt l v phng php chng ta quan st n; do xut hin sai s
chun .
Thng thng, xc nh im cui php chun ngi ta s dng ha cht ph c
kh nng bin i mu ca mnh theo s bin i nng gn im tng ng. Nhng
cht nh vy gi l cht ch th.

8.2 Phn ng v thuc th dng trong phn tch chun

Ty thuc vo loi phn ng dng lm c s cho mi phng php ngi ta chia cc
phng php chun thnh 4 loi: phng php kt ta, phng php trung ha (axit baz), phng php complexon v phng php oxi ha kh. Cc phng php ny khc
nhau v bn cht ca cn bng c s dng, v ch th, v thuc th, v cht chun gc.

8.2.1 Nhng cht chun gc

ng ca kt qu phn tch chun ph thuc rt nhiu vo cht chun gc c
dng thit lp (trc tip hoc gin tip) nng dung dch chun. Cc cht c chp nhn
l cht chun gc tt cn phi tho mn mt lot nhng i hi quan trng:
1. Chng phi c tinh khit cao nht, hn na phi c nhng phng php n gin,
tin cy khng nh tinh khit ca chng.
2. Phi bn, ngha l khng tc dng vi cc cu t ca kh quyn.
3. Khng cha nc hirat. Khng phi l cht ht m hoc c xu hng phong ho kh
lm kh v kh cn.
4. Phi d kim (gi thnh va phi).

5. C phn t gam mol cao. Khi lng cht cn thit chun ha hoc
iu ch dung dch c nng cho s cng ln nu phn t gam ca n cng ln. Khi khi
lng tng sai s ca php cn s gim, phn t gam cng cao c kh nng lm gim sai s
cn cng ln.
Ch c mt s t cht tha mn hoc hu nh tho mn cc yu cu v do s cht
quy cch dng lm cht chun gc b hn ch.
Trong mt s trng hp, thay th cho cht chun th nht phi dng cht km tinh khit
hn. tinh khit ca cht chun th hai cn phi c xc nh bng con ng phn
tch cn thn.
Vic s dng cc t ng cht chun th nht v th hai l ngun gc s bt ng
gia cc nh ha hc. Mt s gi mt s tng i t hp cht c cc tnh cht c k ra
u mc ny l cc cht chun gc v cc cht chun c thnh phn c bit mt cch tin
cy l cht chun th hai. Mt s khc a thch xem tt c cc cht loi bit l cc cht
chun th nht v cc dung dch vi nng bit l cc cht chun th hai. Chng ta chn
h cc thut ng th nht.

8.2.2 Dung dch chun

Dung dch chun l tng phn tch chun cn phi c nhng tnh cht sau:
1. Sau khi iu ch nng ca n phi khng bin i trong thi gian bo qun lu
(trong mt vi thng hoc hng nm), khng cn phi chun ha li.
2. Phn ng nhanh vi cht cn xc nh thi gian ch i sau khi thm tng phn nh
thuc th phi ngn.
3. Phn ng gia thuc th v cht cn xc nh cn phi xy ra hon ton c th
xc nh im cui tho mn.
4. Phn ng gia thuc th v cht cn xc nh cn phi xy ra hp thc, nu khc i th
khng th tnh trc tip khi lng cht cn xc nh.
5. Cn phi c phng php xc nh im tng ng ca phn ng gia thuc th vi
cht cn xc nh, ngha l c phng php xc nh im cui tho mn.
Hin nay, ch c mt s t trong nhng thuc th c s dng tho mn hon ton tt
c cc yu cu .
8.3

im cui trong cc phng php chun

Ngi ta xc nh im cui ca php chun bng cch quan st s bin i mt tnh

cht vt l no im tng ng. C th xc nh im cui theo s bin i mu ca
thuc th, ca cht cn xc nh hoc ca ch th. tm im tng ng ngi ta s dng

s bin i c ca cc tnh cht vt l khc nh th in cc, dn, nhit v ch s khc

x.
S bin i nng trong qu trnh chun
im cui ca php chun xy ra s bin i nng rt ln t nht ca mt trong
cc cht phn ng. Trong phn ln (nhng khng phi l tt c) trng hp, xc nh im
cui ngha l xc nh nhng bin i xy ra vng ln cn im tng ng l c bit
quan trng. minh ho ny trong ct th hai v th ba ca bng 8.1 dn ra nhng d kin
ch r s bin i nng ion hiro v hiroxyl khi chun 50,0 ml dung dch axit clohiric
0,100 M bng dung dch NaOH 0,100 M. nhn mnh rng, chng ta c bit ch ti
nhng bin i nng ng k, nn ta thm vo tng th tch thuc th gy nn s tng
hoc gim 10 ln nng cht phn ng.
lm gim nng ion hiro t 0,100 M n 0,0100 M cn phi thm vo 40,9 ml
kim. h thp nng n 0,00100 M i hi ph thm 8,1 ml. giai on sau, lm
gim nng 10 ln ch cn phi thm vo 0,89 ml ... ng thi quan st thy s bin i
tng t nng ion hiroxyl. T cc d kin ca bng 8.1, ta thy gn im tng ng s
bin i nng cc cht phn ng l cao nht. Trong nhiu trng hp, s xc nh thnh
cng im cui c thc hin nh chnh gi tr ca s bin i . Trn hnh 8.1 dn ra
th bin i c xy dng theo cc d kin ca bng 8.1. Mi chia trn h trc ca th
c gi tr ln ton thang bao trm mt khong ln ca s bin i nng thuc th.
Do , nhng bin i quan st c trong vng chng ta quan tm nht - vng im tng
ng - cn cha c r rng.
a

Bng 8.1 S bin i nng khi chun

Th tch dung dch

NaOH 0,100 M, ml

Nng
H3O+, mol/l

Nng OH
mol/l

pH

pOH

0,0

1,0.101

1,0.1013

1,00

13,00

40,9

1,0.102

1,0.1012

2,00

12,00

49,01

1,0.103

1,0.1011

3,00

11,00

49,90

1,0.104

1,0.1010

4,00

10,00

49,990

1,0.105

1,0.109

5,00

9,00

49,9990

1,0.106

1,0.108

6,00

8,00

50,0000

1,0.107

1,0.107

7,00

7,00

50,0010

1,0.108

1,0.106

8,00

6,00

50,010

1,0.109

1,0.105

9,00

5,00

50,10

1,0.1010

1,0.104

10,00

4,00

51,01

1,0.1011

1,0.103

11,00

3,00

61,1

1,0.1012

1,0.102

12,00

2,00

Nhng d kin trong bng 8.1 ch dng minh ha nn cng d dng hiu rng: khng
c kh nng thu c nhng d kin nh th trong phng th nghim bi v o th tch v
nng dung dch n 6 ch s c ngha thng l iu khng th lm c.
hnh dung r rng hn s bin i trong vng , biu din nng khng phi
dng tuyn tnh m dng logarit s thun li hn. V chng thng nh hn n v nn s
dng logarit m l hp l v v vy hm s din t nng di dng s dng nh.
Logarit m (c s 10) ca nng phn t c bit di dng hm s p. Nhng gi tr pH
v pOH c a ra 2 ct cui ca bng 8.1.

Hnh 8.1
S bin i nng cc cht phn ng khi chun 50,00 ml dung dch HCl 0,0100 M bng dung dch NaOH 0,100 M

V d: Hy tnh hm s p ca mi ion trong dung dch 0,020 M theo NaCl v 0,0054 M

theo HCl.
1.

[H3O+] = 0,0054 = 5,4.103

pH = log[H3O+] = log[5,4.103] = 2,27

Cn nh rng trong kt qu tm c c 3 ch s c ngha xy dng th theo hm
s p (hnh 8.2) mc d i vi [H3O+] ch c 2 ch s.

2.

[Na+] = 0,020 = 2.102

pNa = log(2.102) = 1,70.

3.

[Cl] = 0,020 + 0,0054 = 0,0254

pCl = log(2,54.102) = 1,6.

V d: Hy tnh [Ag+] trong dung dch nu pAg = 6,372.
pAg = 6,372 = 7,000 + 0,628
[Ag+] = antlog(7,000).antlog(0,628) = 107.4,246 = 4,25.107.
Nu nng ion ln hn 1 mol/l, hm s p ca n s l s m. V d, trong dung dch
HCl 2,0 M:
[H3O+] = 2,0 ion.g/l
pH = log[H3O+] = log2,0 = 0,30.
Nu nhng gi tr pH v pOH c dn ra bng 8.1 c mang ln th theo th tch
thuc th thm vo th thu c ng cong cho bc tranh r rng hn v s bin i nng
xy ra trong dung dch gn im tng ng: y quan st thy s tng t ngt pH
v s gim tng ng pOH.
Nhng ng cong tng t nh ng cong c din t trn hnh 8.2 c gi l
ng chun . th c xy dng theo nhng d kin tng t i vi cc php chun
oxi ha kh, kt ta hoc complexon cng c nhng c tnh y. Trong cc chng sau s dn
ra v bn lun nhng v d in hnh v ng chun .

Hnh 8.2
ng chun 50,0 ml dung dch HCl 0,100 M bng dung dch NaOH 0,100 M

iu ch ln nht i vi nh ha hc phn tch l dng ng chun v c bit l

gi tr bc nhy, trong trng hp ny l bc nhy pH im tng ng, bi v chnh
yu t quyt nh c th xc nh im cui ng v d dng n mc no. C th d dng
pht hin s bin i tnh cht vt l v do pht hin chnh im cui, im thng gn
lin trc tip vi gi tr v tc bin i hm s p. Theo l thng, xc nh im cui d
hn c l khi hm s p bin i ln trong mt vng nh th tch thuc th.