TRNG I HC NNG LM HU

D N HP TC VIT NAM H LAN

BI GING
HO V C PHN TCH













Ngi bin son: Phan Th Hi













Hu, 08/2009


1

MC LC



Trang
Chng 1: i cng v ho hc phn tch.......................................................2
Chng 2: Phng php phn tch trng lng...............................................4
Chng 3: Phn tch th tch.................................................................................14
Chng 4: Phng php chun axit - baz..................................................22
Chng 5: Phng php chun kt ta.........................................................35
Chng 6: Phng php to phc .......................................................................45
Chng 7: Phng php chun oxy ho - kh............................................52
Chng 8: Phn tch cng c.................................................................................66
Chng 9: Sai s trong ho hc phn tch..........................................................71

















2

Chng 1:
I CNG V HO HC PHN TCH

1.1. M u.
Ho hc phn tch l mn khoa hc v cc phng php xc nh thnh phn
nh tnh v nh lng ca cc cht v hn hp ca chng.
Ho hc phn tch ng vai tr quan trng i vi s pht trin ca cc mn
hc khc cng nh cc ngnh khoa hc khc nh cc lnh vc ca cng ngh, sn
xut v i sng x hi. Trong lnh vc Nng Lm Ng ho hc phn tch c mt
tm quan trng ng k, n c mt trong sut qu trnh sn xut (kim nghim vt
liu, bn thnh phm, sn phm cui cng) bo qun lu thng v s dng cc loi
thuc trong Nng, Ng, Y. Cc phng php phn tch s dng rt phong ph v a
dng trong cc lnh vc khc nhau: vt l, ho hc, sinh hc.
Do c tm quan trng nh vy nn mt lot cc chuyn ngnh ca khoa hc
phn tch ra i v ngy cng pht trin nh: phn tch mi trng, phn tch
khong liu, phn tch hp kim, phn tch dc phm, phn tch thc phm
Da trn bn cht ca phng php phn tch ngi ta c th chia ra cc nhm
phng php phn tch:
- Phng php ha hc: l phng php da trn nhng phn ng ho hc. V
d: phn ng acid base, oxy ho - kh, kt ta ho tan, to phc.
- Phng php ho l, vt l: phng php vt l da trn nhng hin tng v
qu trnh nh phng php quang ph, phng php so mu, vt l ht nhn,
- Phng php sinh hc: da trn nhng hin tng ca cuc sng (trao i cht,
tng trng, c ch ca sinh vt), th d nh phng php phn tch vi sinh vt l
da vo qu trinh trao i cht ca vi sinh vt. Bng phng php vi sinh vt ngi
ta nh lng cc thuc khng sinh, khng nm, vitamin,
Khi phn tch mt i tng no nh phn tch phi thc hin cc bc sau:
a. Chn phng php phn tch thch hp v xc nh cc vn cn gii quyt.
thc hin bc ny nh phn tch cn ch tm quan trng, kinh t ca cng
vic phn tch, tnh kh thi ca phng php phn tch.
b. Chn mu i din l mu phn tch ng nht cho thnh phn ca i tng
nghin cu.
c. Tch cht: phn tch cc mu c thnh phn phc tp thng loi tp cht
hoc tch cht cn phn tch ra khi hn hp ca cc hp cht khc.
d. Tin hnh o cc cht cn phn tch.: S dng cc dng c, my mc, thch hp
phn tch cc cht cn phn tch.
e. Tnh ton v x l kt qu phn tch: Cc d liu thu c x l theo ton thng
k nh gi tin cy ca kt qu o c. Cc bc trn lin quan mt thit vi
nhau v nh hng ln nhau. Trong thc t, tu theo tng trng hp c th, cc
bc tin hnh trn c n gin hoc b qua mt s bc, hoc thc hin ng
cc bc trn.

3
1.2. Ly mu v x l mu phn tch:
Nhiu v quan trng ca ho phn tch l ly mu v x l mu, y l giai on
u tin ca cng vic phn tch, giai on ny rt cn thit ngay c phng php
dng my, v vic s dng my ch giai on cui cng. Do vy cn phi quan
tm cao n cng tc chun b mu phn tch, trong cng tc chun b mu gm
cng vic ly mu v x l mu sao cho ng quy cch v ng yu cu phn tch.
1.2.1. Ly mu:
- Vic ly mu nhm iu ch cht tinh khit ho hc: i vi cht rn phi tinh
ch li bng phng php kt tinh hay thng hoa, cn cht lng phi chng ct phn
on.
- Cn trng hp hay gp nht trong thc t l xc nh thnh phn trung bnh
ca mt lng ln nhng phm vt nh qung, t, , sn phm, m thnh phn
ho hc ca chng khng ng nht, do vy nhim v quan trng nht ca ly mu
trung bnh (mu i din) l mu cha thnh phn v t l hm lng ging nh vt
th cn phn tch.
Vic ly mu trung bnh (mu i din) phi tin hnh theo mt quy nh cht
ch, tu tng loi i tng phn tch m ta ly mu, mu ng nht ly trc tip
bt k v tr no, i vi mu khng ng nht tu thuc vo lng c th ly c
bao gm cng nhiu cng tt, nhng thnh phn nh ly mt cch t nhin cc a
im khc nhau, mu ny thng khng c s dng ngay v s lng qu ln,
cn phi s l. C mt phng php thng dng l: nghin nh, trn u mu dung
thut chia bn loi bt mu, trn u n khi no mu cn chng 25g em i
phn tch, mu phi c bo qun cn thn, trnh nhim mi trng xung quanh.
V d mu t phi bo qun trong mi trng HCl trnh Fe(II) b oxyho thnh
Fe(III).
1.2.2. Cch lp h s mu:
Mu ly xong phi chia mu thnh hai phn, mt phn phn tch, mt phn gi
li trnh mt mu, cch lp h s mu:
- Ghi ngy ly mu.
- Ngi ly mu.
- a im ly mu.
- Cch ly mu.
- Ch tiu cn phn tch ca mu.
Tt c cng vic ny phi cn thn trnh nhm ln.
1.2.3. Cng ph mu:
Cng vic cng ph mu l chuyn cc cht cn phn tch t cht rn sang
dung dch ri a v trng thi thun tin cho vic o.
C th ho tan trc tip bng nc, axt hay hn hp axt HCl + HNO
3
,
H
2
SO
4
+ HClO
3
, H
2
SO
4
+ H
3
PO
4
dung dch kim, dung dch cht oxy ho -
mnh nhng mc cng ph cng tu thuc vo ch tiu phn tch. Cc ch
tiu: m, pH, ln d tiu, ln tng s, m, dng cc khong ho thch hp
cng ph.

4
V d: phn tch Kali ch tiu dng dung dch amoni axetat 1N lm dung
dch chit sut, cn kali tng s dng hn hp cc axit H
2
SO
4
+ HClO
4
+ HF.
Trong vic cng ph mu c gng trnh dng cng t ho cht cng tt, ho
cht cng ph cng n gin cng tt trnh s nhim bn do ho cht, trnh tn
hi dng c v sc kho ca ngi phn tch.
Phng php cng ph thng dng hai phng php: Cng ph t v cng
ph kh:
Cng ph t: Cho mu tc dng vi dung dch ho cht nhit thng
hoc un nng. Phong php ny nhanh, n gin nhng lm c t mu, d b
bn mu do ho cht cng ph.
Cng ph kh: nung mu vi ho cht nhit xc nh ph hp vi tnh
cht ca mu. Phng php ny cn dng c iu chnh nhit , cng ph chm
thi gian cn nhiu, lng ho cht cn t, sn phm sau khi cng ph c ho tan
vo nc, dung dch axt long, hay kim long.
Cng nh vic ly mu, vic cng ph mu c vai tr quyt nh n cht
lng phn tch, nn vic cng ph mu phi ng quy trnh cho tng i tng
tng ch tiu phn tch.





















5
CHNG 2:
PHNG PHP PHN TCH TRNG LNG

Phng php phn tch trng lng l mt trong nhng phng php nh
lng chnh xc nht. chnh xc c th t ti 0,1% hoc cao hn. Tuy nhin n
i hi thi gian v nhng ng tc phc tp. Phng php phn tch trng lng
thng c dng trong nhng trng hp hm lng cht cn phn tch tng i
ln, hoc cn t n chnh xc cao nh: khi kim tra cht lng sn phm, nng
dung dch chun chng hn.
2.1 Nguyn tc:
Qu trnh phn tch trng lng bt u t vic cn mt lng chnh xc
(thng gi l lng cn) mu phn tch, ri ha tan thnh dung dch. Nu i
tng phn tch l dung dch, th ch cn ly mt th tch chnh xc phn tch.
Sau lm kt ta cht cn phn tch di dng mt hp cht kh tan hoc i khi
di dng n cht. Lc, ra sch v sy hoc nung chuyn thnh hp cht bn c
thnh phn ha hc xc nh. Cui cng da vo khi lng ca kt ta sy hoc
nung, tnh hm lng cht cn phn tch.
Nguyn tc: Phng php phn tch khi lng l mt phng php nh
lng ha hc, da vo vic cn khi lng ca sn phm hnh thnh sau phn ng
kt ta bng phng php ha hc hay vt l, kt ta c thnh phn cng thc ha
hc xc nh t suy ra hm lng cht cn phn tch.
Phng php ny cho php xc nh hu ht cc nguyn t trong t nhin, c
chnh xc v tin cy cao, tuy nhin tn thi gian, i hi thao tc phc tp.
2.2 Cc bc tin hnh:
a. Chn mu v gia cng mu.
b. Chuyn mu vo trng thi dung dch v tm cch tch cht cn phn tch ra
khi dung dch ( lm kt ta , hay bay hi. . . ) lc v ra kt ta.
c. Chuyn ha sn phm tch bng cc bin php thch hp nh sy , nung.
d. Cn v tnh ton kt qu.
Dng c c bn trong phn tch khi lng l cn phn tch, ngay trong giai
on u n giai on cui. Nh vy cn l mt trong nhng ng tc chnh xc
nht ca qu trnh phn tch, nn cng vc u tin ca ngi phn tch l phi nm
vng v nguyn tc cng nh s dng cn ni chung.
2.3 Phn loi phng php:
Ty theo cch tin hnh ngi ta chia cc phng php trng lng thnh
cc phng php sau:

6
a. Phng php kt ta khi lng.
Phng php ny dng phn ng kt ta tch cht cn phn tch ra khi
dung dch phn tch. Sau kt ta c lc, ra , sy , nung n khi lng khng
i v em cn tnh ton kt qu.
V d : nh lng ion SO
2
4

th lm kt ta di dng BaSO
4
ra sch sy
v nung. Cn khi lng BaSO
4
t tnh ton kt qu phn tch.
b. Phng php y ( hay tch ).
Tch cc cht cn phn tch v trng thi t do lc, ra v cn khi lng
cht tch t xc nh hm lng % cht cn phn tch.
V d : nh lng vng trong hp kim, ngi ta ly mu i din hp
kim , em ha tan mu trong mt lng thch hp nc cng thy ( HCl +
HNO
3
) chuyn hon ton mu thnh dung dch, em ch ha dung dch vi
thuc th thch hp chuyn Au (III) thnh Au kim loi , lc ra sy n khi
lng khng i. Cn Au t xc nh hm lng vng trong mu.
[AuCl
4
]
-
+ FeSO
4
Au + Fe(SO
4
)
3
+ Cl
-

c. Phng php bay hi.
Ly mu phn tch ri x l bng nhit hay thuc th thch hp, cht
phn tch bay hi ra v xc nh hm lng cht cn phn tch da trn tng hay
gim khi lng ca bnh sau khi bay hi.
Phng php ny thng xc nh cc hp cht hu c.
C
x
H
y
O
z
bg CO
2
+ cg H
2

T tnh thnh phn %O; %H ; %C suy ra hm lng cht cn phn
tch. Trong cc phng php trn, phng php kt ta khi lng thng c s
dng , bi v d lm, d to kt ta. Do vy chng ta s i su vo phng php
ny.
2.4 Phng php phn tch kt ta khi lng.
2.4.1 Nguyn tc:
Nguyn tc ca phng php kt ta khi lng l chuyn cht cn phn tch
thnh dung dch, ri lm kt ta cht cn tm di dng mt hp cht kh tan no
. Lc nung kt ta n khi lng khng i. T suy ra hm lng cht cn
phn tch
Phng php kt ta khi lng gm cc cng on sau:
Cn mu ( lng cn ) Ha tan thnh dung dch + Thuc th Kt
ta Lc, ra kt ta Sy hoc nung Cn v tnh ton kt qu suy ra hm
lng cht cn phn tch.

7
Trong qu trnh sy hoc nung mt s cht thng b bin i v tnh cht ha
hc do vy cn phi phn bit dng kt ta v dng cn t c nhng yu cu
c th i vi tng dng:
Dng kt ta: l dng hp cht tch ra khi dung dch di tc dng ca
thuc th.
Dng cn: l dng hp cht c thnh phn ha hc xc nh c em cn
sau khi sy v nung.
Tt c cc cng on trn u nh hng trc tip n chnh xc ca kt qu
phn tch, trong cng on lm kt ta c nh hng ln nht. Do vy vic chn
kt ta, lng kt ta, iu kin thc hin kt ta. . . s m bo chnh xc cho
php phn tch.
V vy c chnh xc cao ngi phn tch cn phi chn dng kt ta, dng
cn tha mn cc yu cu sau.
2.4.2 Yu cu dng kt ta, dng cn.
2.4.2.1. Yu cu dng kt ta.
Khng phi bt k mt kt ta no cng c s dng trong phng php kt
ta khi lng, m cc kt ta phi tha mn yu cu sau.
a. Dng kt ta phi rt t tan m bo cho s kt ta xy ra hon tan
V d: ion Ba
2+
c th to kt ta vi mt s thuc th sau cho cc tch s tan khc
nhau.
BaCrO
4
c T
BaCrO
4

= 1,6.10
-7

BaCO
3
c T
3
BaCO
= 8,0.10
-9

BaC
2
O
4
c T
4 2
O BaC
=2,4.10
-10

BaSO
4
c T
4
BaSO
= 1,1.10
-10

Do cn phi chn BaSO
4
lm kt ta do tch s tan ca hp cht ny l
nh nht. Tuy nhin dng kt ta khng phi ch ph thuc vo tch s m cn ph
thuc vo tan ca kt ta v cn nhiu yu t nh hng vo tatn ca kt ta
sau y chng ta xt mt s yu t chnh.
- Tch s tan nh hng n tan kt ta.
Nu kt ta MXn trong dung dch c th tan ra :
MXn M
n+

+ nX
-

C tch s tan l
T
MXn
= [M
n+
][X
-
]
n

Gi s c s phn t gam MXn tan trong 1 lt dung dch th:

8
Nng ion M
n+
l s iong/l
Nng ion X
-
l ns iong/l
Ta c : T
MXn
= s. (ns)
n

= n
n
.
s
n+1

Trong iu kin ang xt tr s ca s trng vi tan ca kt ta, do
tan s s l :
S =
n m
n
MXn
n
T
+
(2.1)
tan kt ta t l thun vi tch s tan, do mun kt ta hon ton phi chn
kt ta no c tch s tan nh nht.
- nh hng ion chung n tan kt ta
iu kin chn tch s tan nh nht ch p dng trong trng hp dung dch phn
tch ch cha ion cn xc nh. Cn trong trng hp dung dch c mt cc ion
khc, c th gy cn tr cho vic lm kt ta ca ion chnh th lc ta phi kt hp
vi iu kin c th chn kt ta.
V d : Khi xc nh ion Pb
2+

c th c cc kt ta sau hnh thnh :
PbCO
3
c T
3
PbCO
= 1,0.10
-14

PbCrO
4
c T
4
PbCrO
=1,0.10
-13

PbSO
4
c T
4
PbSO
= 1,0.10
-8

Tuy nhin nu trong dung dch ch c cha mt mnh ion Pb
2+
th ta chn dng
kt ta l PbCO
3
v c tch s tan nh nht. Nhng trong dung dch phn tch c mt
ng thi cc ion Cu
2+
; Bi
2+
phi chn kt ta PbSO
4
mc d c tch s tan ln
nht, bi v cc ion ny khng b kt ta theo khi dung dch thuc th.
- nh hng ca pH mi trng v cht to phc n tan ca kt ta
Trong mi trng nc cc ion M
n+
, X
-
cng c th tham gia phn ng thy phn.
S thy phn s ph thuc vo pH mi trng.
-Khi pH tng cation tham gia phn ng thy phn mnh
-Khi pH gim anion tham gia phn ng thy phn mnh
M
n+

+ H
2
O = M(OH)
(n-1)
+ H
+

M
(n-1)+

+ H
2
O = M(OH)
(n-2)
+ H
+
. . . . .
.
M(OH)
n-1
+ H
2
O = M(OH)
n
+ H
+

Hoc:
X
m-
+ H
2
O = HX
(m-1)
+ OH
-

9
HX
(m-1)-
+ H
2
O = HX
(m-2)-
+ OH
-
. . . . .


H
m-1
X
-
+ H
2
O = H
mX
+ OH
-
Nh vy s thu phn hay to phc u dn n s gim nng cc ion to kt
ta. Do lm tng s ho tan ca kt ta do tch s tan t l vi nng .
- nh hng ca cc yu t khc n tan kt ta:
tan kt ta cn ph thuc nhiu yu t khc nh : nhit , kch thc ht kt
ta, nng cht in ly. . . Do khi tin hnh kt ta phi lm ng quy trnh
phn tch.
b. Kt ta phi c cu to nh th no d lc, d ra. Cc kt ta phi c
tinh th ln c li cho vic lc, khng bt giy lc, c tng din tch b mt nh, t
hp th cc cht bn trong dung dch, d ra sch
c. Dng kt ta phi c chuyn d dng v hon ton sang dng cn
2.4.2.2. Yu cu dng cn:
Dng cn l dng em sy nung n khi lng khng i v c thnh phn
ho hc xc nh.
a. Dng cn phi c cng thc ho hc xc nh. t khi lng ca cht rn
c nhng kt ta ng ng vi cng thc ho hc xc nh ca n nh BaSO
4
.
Nhng vi Fe(OH)
3
khng dng c trong dng cn v cng thc ng ca n l:
Fe
2
O
3.
xH
2
O, tu thuc vo kt ta m Fe(OH)
3
c mt lng nc khc nhau, nh
vy phi nung mt nc cng thc mi ng ng thnh phn ho hc ca n l Fe-
2
O
3
.
b. Dng cn phi bn v phng din ho hc: Khng hp th hi nc, kh CO
2

trong khng kh, khng b oxy ho-kh hoc b phn hu nhit cao. . . Phi c
yu cu ny th yu cu trn mi m bm.
c. Hm lng nguyn t cn tm trong dng cn cng nh cng tt, trnh sai s
cn.
d. Tha s chuyn F ng vi dng cn cng nh cng tt. Khi sai s ( ong,
cn. . . ) cng t nh hng n kt qu phn tch.
Qua cc yu cu trn i vi dng kt ta, dng cn ta thy vic chn dng
kt ta, dng cn l rt quan trng trong phng php kt ta khi lng v n
quyt nh chnh xc cng nh tc ca php phn tch.
2.4.3 Cc yu t nh hng n qu trnh kt ta.
2.4.3.1. S to dung dch keo:

10
Phn dung dch keo trong ho hc i cng. y cng l ngun gy ra sai
s cho phng php, khng lc, khng ra kt ta c, vic khc phc l phi lm
kt ta theo ng k thut lm kt ta.
2.4.3.2. S cng kt:
Trong qu trnh phn tch cc kt ta c hnh thnh, thng ko theo vo
cu trc ca mnh cc tp cht ( cc ion l ). Khi tp cht cng kt ta ng thi vi
kt ta chnh, mc d nng ca chng cha t ti bo ho c gi l hin
tng cng kt. y l ngun sai s nghim trng nht cho phn tch kt ta khi
lng.
Cc nguyn nhn gy nn s cng kt l : s hp th b mt, s kt vn, s to
tinh th hn hp.
S cng kt do hp th xy ra khi kt ta chnh dng keo trong s d tha
ca kt ta. Cc ht keo hp th ion hot ng ca thuc th s dn n s hp th
cc ion tri du khc. V d: Kt ta BaSO
4
trong iu kin d SO
4
-2
s hp th cc
ion dng. Trong trng hp ny thc t cho thy ion no tp mui c tan nh
hn vi thuc th s b hp th nhiu hn, nh BaSO
4
ni trn hp th nh sau :
Na
+
<K
+
<Ca
2+
<Pb
2+
. khc phc cn tin hnh kt ta vi dung dch long v
thuc th long.
S cng kt do hin tng kt vn gy bn c hc kt ta, nguyn nhn khi
tin hnh kt ta mt phn cht tp b kt ta bao bc. Hin tng ny thng
gp khi kt ta vi dung dch c v kt ta nhanh. loi tr s cng kt ny cn
tin hnh kt ta li.
S cng kt do hin tng to tinh th hn hp xy ra khi bn knh ion ca
ion kt ta chnh v ion tp khng khc nhau nhiu ( sai khc nh hn 10-15%).
Lc ny cc ion tp c th thay th cho ion kt ta chnh trong mng tinh th. V d
: KMnO
4
c th thay th cho BaSO
4
nn khi kt ta BaSO
4
trong iu kin mi
trng cha KMnO
4
s thu c tinh th c cha KMnO
4
, loi cng kt ny khng
th loi b c bng cch kt ta li m ch c th dng phng php che hoc
kh cc ion tp i. V d: kh ion MnO
4
-
v ion Mn
2+
.
Trong phn tch s cng kt khng phi lc no cng gy hi cho qu trnh kt
ta. Vic s dng hin tng ny cng c ngha to ln khi tin hnh phn tch cc
mu vt c hm lng nh, li dng hin tng cng kt ngi ta gom cc cht
cn phn tch. V d: xc nh hm lng Pb
2+

trong mu nc, ngi ta cho
Ca(OH)
2
( nc vi trong) lm kt ta Ca
2+

di dng CaCO
3
trong iu kin ny
ion Pb
2+
s b kt ta theo, sau ho tan vo CH
3
COOH ri phn tch Pb
2+
theo
phng php thng thng. Da vo hin tng cng kt ta c th lm tng nng
cc cht cn phn tch ln n hng ngn, hng vn ln.
Ngoi hin tng cng kt, thc t cn gp mt s hin tng kt ta sau lm
bn kt ta chnh, tc l cc tp cht iu kin thng khng to c kt ta

11
nhng khi kt ta chnh hnh thnh cc tp cht s b kt ta theo. V d: MgC
2
O
4

khng to kt ta nhng khi CaC
2
O
4
cng kt ta, lu trong dung dch MgC
2
O
4
b kt ta theo. khc phc cn lm kt ta nhanh.
2.4.4 Mt s k thut lm kt ta.
tho mn iu kin kt ta cn ht sc ch n cc k thut sau:
2.4.4.1 Chn thuc th lm kt ta:
+ Thuc th phi d loi i khi lc v khi ra. V d: lm kt ta Ba
2+
dng
H
2
SO
4
khng dng NaSO
4
v H
2
SO
4
d loi i khi lc, khi ra.
+ Thuc th phi c tnh chn lc cao, dng vi mt lng d thuc th,
nh vy tan kt ta s gim i nhiu.
Tuy nhin cn lu mt s thuc th s tan trong thuc th d, trong trng
hp ny phi tnh ton sao cho lng thuc th phi va kt ta xy ra hon
ton.
2.4.4.2 K thut lm kt ta:
Tu theo bn cht ca kt ta ( dng tinh th, dng v nh hnh ) m c cch
lm kt ta khc nhau.
- Kt ta tinh th : s to thnh kt ta bao gm 2 giai on:
S to mm kt tinh
Cc mm kt tinh ln dn ln.
Mun tinh th c ht ln, cn tng cng cho giai on sau v hn ch giai on
u, c nhiu phng php nh lm kt ta khi dung dch, long, thuc th long.
Hoc lm tng tan kt ta bng dung dch nng, thuc th nng v pH thp. . .
Tuy nhin thng hay s dng nht l phng php mui kt ta:
Ngi ta ngm kt ta trong thuc th mt thi gian nht nh, khong vi gi
hoc lu hn, cc tinh th nh s tan ra, cc tinh th ln s ln dn ln, nguyn nhn
do cc tinh th nh bao gi cng c tch s tan ln hn, nn tan mt phn trong
dung dch, nh lm tng nng ion trong dung dch, to iu kin cho cc tinh
th ln kt tinh thm, lm cc tp cht hp th trn b mt ca kt ta cng gim,
kt ta tr nn tinh khit hn, d lc, d ra.
- Kt ta v nh hnh: c to ra do s ng t ca cc dung dch keo, c
th gi l pecty ho do phi lm nh sau:
Ngc li vi vic lm kt ta tinh th, khi lm kt ta v nh hnh cn phi
tin hanh khi dung dch cn nng, c, kt ta trong s c mt ca cc cht in ly
mnh, lm trong iu kin ny kt ta s chc hn, d lc v gim s nhim bn do
hp th. Khi lm kt ta xong cn pha long gp i bng nc nng v khuy
mnh, lc ra ngay lu kt ta qunh li kh ra.

12
2.4.4.3 Lc v ra kt ta
- Lc kt ta quan trng nht l chn c giy lc thch hp, trnh vic lt
kt ta hoc bt giy lc. Giy lc c chia lm ba loi theo kch thc ca
giy.
- Loi l nh ( giy lc bng xanh) lc ht c nh.
- Loi l trung binh ( giy lc bng xanh, trng hoc bng vng) lc ht c va.
- Loi l ln ( giy lc bng ) lc ht c ln.
- Ra kt ta: Mc ch loi tp cht trn b mt kt ta, trong qu trnh ra
kt ta phi chn dung dch ra v cch ra cho thch hp, c th chia ra cc
trng hp sau:
- Nu kt ta hnh thnh thng c hin tng to dung dch keo, dung dch ra
phi l cht in gii, d bay hi khi nung.
V d : Al(OH)
3
; Fe(OH)
3
dung dch ra l NH
4
Cl v NH
4
NO
3

- Nu thuc th l cht d bay hi hoc d b phn hu khi sy khi nung. Dng
dung dch ra c cha thuc th, ra bng cch ny hn ch c s tan ca kt
ta.
V d: Ra kt ta AgCl bng dung dch HCl long.
- Nu kt ta thng tham gia phn ng thu phn, dng dung dch ra c kh
nng ngn nga s thu phn.
V d : Ra MgNH
4
PO
4
bng dung dch cha NH
4
OH ngn nga s thu phn.
- Cc trng hp cn li ch ra bng nc ct.
Ch : Khi ra cn phi ra nhiu ln, khi ht dung dch ra mi tip, ra nh
vy mau sch v tnh c nng dung dch ra sau khi ra n ln.
Cn = Co
R V
R
n
|
|
.
|

\
|
+
(2.2)
n : s ln ra
V: th tch dung dch ra
R: th ch dung mi b kt ta hp th
Co: nng cht b hp th khi cha ra
Cn: nng cht b hp th sau khi ra n ln
2.4.4.4 Sy v nung kt ta: mc ch chuyn kt ta v dng cn.
-i vi kt ta c dng kt ta trng vi dng cn th cn sy nhit 95
o
n
105
o
.

13
-Cn cc loi kt ta khc sau khi sy kt ta cn phi nung nhit xc nh,
n khi khi lng khng i, nhit nung phi chnh xc kt ta chuyn sang
dng cn m khng lm cho dng cn tip tc bin i.
2.4.5 Tha s chuyn F v cch tnh kt qu trong phn tch kt ta khi lng
2.4.5.1. Tha s chuyn F
Thng thng dng cn khng phi l kt qu phn tch m t dng cn
chng ta suy ra hm lng cht cn phn tch.
V d: Xc nh khi lng Si theo dng cn SiO
2
. Sau qu trnh phn tch cn
c khi lng dng cn l : b=0,2450g.
Theo qui tc tam xut ta c : C 28g Si c trong (28+16.2)g SiO
2

Vy xg Si c trong 0,2450g SiO
2

X=
2 . 16 28
28
+
. 0,2450 = 0,1143
Vy t s
2 . 16 28
28
+
c gi l tha s chuyn F.
nh ngha : Tha s chuyn F l t s gia phn t gam ( hay ion gam)
nhn vi h s tng ng ca cht cn xc nh v phn t gam ca dng cn.
F=
dc
x
mM
nM
(2.3)
n,m l h s t l m bo cho nguyn t ca nguyn t cn xc nh dng
xc nh v dng cn bng nhau.
V d : Nu dng cn l Mg
2
P
2
O
7
( manh piro phtphat ) cn dng cn xc
nh l : Mg ; MgO tha s chuyn tng ng.
F
Mg
=
7 2 2
. 2
O P Mg
Mg
M
M
=
16 . 7 23 . 2 24 . 2
24 . 2
+ +
= 0,185
F
MgO
=
7 2 2
. 2
O P Mg
MgO
M
M
=
16 . 7 31 . 2 24 . 2
) 16 24 .( 2
+ +
+
= 0360
i khi dng cn khng cha nguyn t cn tm.
V d: Khi nh lng nit trong mui amni clorua. Ngi ta lm kt ta
nguyn t cn tm di dng (NH
4
)PtCl
6
sau lc, ra nung thnh Pt kim loi
dng cn. H s chuyn lc ny c tnh.
F=
Pt
N
M
M . 2
=
195
14 . 2
= 0,1435
ngha : Tha s chuyn F cho bit ng vi 1 gam dng cn c bao nhiu
gam cht cn xc nh.

14
2.4.5.2. Cch tnh kt qu theo tha s chuyn F.
Vi khi lng mu ban u ca nguyn t cn tm A l a gam, sau qu trnh
phn tch khi lng dng cn thu c l b gam.
- Khi lng cht A nguyn cht c trong mu;
m
A
= F. B (2.4)
- Hm lng % ca A c trong mu :
%A = F.
a
b
.
v
V
100% (2.5)
2.4.6 Mt s ng dng c th.
1. Xc nh ion SO
4
2-
.
Dng kt ta v dng cn u l BaSO
4
.
Mu phn tch c axit ho n pH=4 bng HCl lm kt ta ion SO
4
2-

Bng dung dch BaCl d. Trong iu kin ny ion CO
3
2-
, PO
4
3-
khng gy
nh hng n kt qu phn tch, kt ta sau khi c ra sch bng nc ct em
nung nhit 800
o
C n khi lng khng i v cn. F=0,4116.
2. Xc nh ion Cl
-

Dng kt ta v dng cn u l AgCl.
Mt mu phn tch c axit ho bng HNO
3
n pH=1 v lm kt ta Cl
-

bng AgNO
3
, kt ta AgCl ra sch, sy, nung nhit 140
o
C v cn. Trong
phng php ny cc ion CO
3
2-
, PO
4
3-
khng nh hng n kt qu phn tch.
3. Xc nh ion PO
4
3-
.
Dng kt ta MgNH
4
PO
4
dng cn Mg
2
P
2
O
7
.
Cho vo dung dch phn tch c axit ho bng HCl vi thuc th
MgCl
2
+ NH
4
Cl sau dng NH
4
OH iu chnh pH mi trng n khi kt ta
hon ton ion PO
4
3-
di dng MgNH
4
PO
4
.6H
2
O. kt ta hon ton dng d
NH
4
OH, kt ta c ra sch bng NH
4
OH 5% v sau khi sy kh th nung nhit
900
o
C chuyn hon ton sang dng cn Mg
2
P
2
O
7
. F=0,8535. Trong trng
hp c cc ion Al
3+
, Fe
3+
mu cn lm kt ta di dng MgNH
4
PO
4
trong mi
trng cha ion xitrat ngn nga s to kt ta FePO
4
, AlPO
4
.
4. Xc nh ion Fe
3+
.
Dng kt ta Fe(OH)
3,
dng cn Fe
2
O
3
.
Cho vo mu phn tch mui NH
4
Cl hay NH
4
NO
3
lm cht in gii v kt
ta Fe
3+
t dung dch nng bng lng d thuc th NH
3
long (1:3) lm kt ta
Fe(OH)
3
, kt ta c lc, ra bng dung dch nng NH
4
NO
3
1% hay NH
4
Cl v sau
nung nhit 1000
o
C, chuyn ton b Fe(OH)
3
sang Fe
2
O
3
. F=0,6994.

15
5. Xc nh ion Al
3+
.
Dng kt ta Al(OH)
3
, dng cn Al
2
O
3
.
Cho vo mu phn tch mui NH
4
Cl hay NH
4
NO
3
lm cht in gii, ri kt
ta Al
3+

t dung dch nng bng thuc th NO
3
long (1:3) vi pH dung dch t 5-9,
kt ta Al(OH)
3
c lc ra bng dung dch nng NH
4
NO
3
1% hay NH
4
Cl, sau
nung nhit 1000
o
C, chuyn ton b Al(OH)
3
sang Al
2
O
3
. F=0,5293.
























16

CHNG 3:
PHN TCH TH TCH

3.1. Nguyn tc:
3.1.1 Nguyn tc
Phng php th tch hay cn gi l phng php chun . L phng php
da trn vic o chnh xc th tch dung dch thuc th ( bit nng chnh xc
hay chun) cn thit phn ng va vi dung dch phn tch. T lng tiu
tn trn ca thuc th tnh ra hm lng cht cn phn tch c trong mu.
Dung dch c nng chnh xc bit trc gi l dung dch tiu chun.
Qu trnh tin hnh:
xc nh nng ca mt cht cn phn tch X bng thuc th R c nng
chnh xc N
R
( vi iu kin X phn ng ha ton vi thuc th R) ri dng
buret nh t t thuc th R xung bnh tam gic c cha V
X
ml dung dch X. Trong
bnh s xy ra phn ng.
X + R P
Tip tc nh R vo X n khi no phn ng t n trng thi cn bng (tc
t n im tng ng) kho buret li c th tch tiu tn ca thuc th R trn
buret.
T cc gi tr: V
R
, N
R
, V
X
xc nh c nng cht cn xc nh X.
Qu trnh dng buret cho t t R vo X gi l qu trnh chun .
V d: Mun nh lng mt dung dch NaOH, ngi ta cho mt dung dch
HCl 0,1N (dung dch tiu chun) ln buret v nh t t vo 10 ml dung dch NaOH
c thm cht ch th mu. Khi ch th chuyn mu th ngng nh lng. c trn
buret thy th HCl 0,1N dng ht l 9,50 ml. Vy nng ca dung dch NaOH l
0,1. 9,5/10 = 0,095N.
NaOH + HCl = NaCl + H
2
O
3.1.2. Mt vi nh ngha quan trng.
a. im tng ng:
Trong qu trnh chun , khi lng thuc th cho vo tng ng ho hc
vi lng cht cn xc nh, ni cch khc, khi s ng lng gam thuc th cho
vo bng s ng lng gam cht cn xc nh th ta ni h t ti im tng
ng. cng chnh l im m ti cht cn xc nh tc dng va vi
dung dch tiu chun.

17
V d: Khi chun HCl bng NaOH:
NaOH + HCl = NaCl + H
2
O
Khi s ng lng NaOH dng ht bng s ng lng HCl, lc trong
h HCl dc trung ho ht bng NaOH, trong dung dch ch c nc v NaCl,
pH = 7. Vy im tng ng y ng vi pH = 7. gip ta pht hin im
tng ng ngi ta thng dng cht ch th mu.
b. Cht ch th mu (Cch xc nh im tng ng).
Trong phn tch th tch, vn quan trng l phi c bin php xc nh c
im tng ng, ngha l phi bit lc no phi dng chun khi cho thm
thuc th vo, n gin v hay dng nht l cht ch th mu.
- Cht ch th l nhng cht c kh nng pht ra cc tn hiu nh: s bin i
mu, s to kt ta, s pht hunh quang . . . hoc gy ra mt du hiu g c
bit ln cn im tng ng bo hiu cho ta bit kt thc qu trnh
chun .
V d: - Khi xc nh Cl
-
bng dung dch tiu chun AgNO
3
dng ch th
K
2
CrO
4
.
- Xc nh Cu
2+
bng phng php Iod Thiosunfat dng ch th h tinh
bt.
c. im kt thc.
Thi im m ti cht ch th gy ra nhng tn hiu khin cho ta kt thc
qu trnh chun .
Thng thng im kt thc khng bao gi trng im tng ng nn gy
sai s cho php xc nh c gi l sai s ch th, v vy phi chn ch th nh th
no sai s ch th nm trong mt phm vi sai s cho php cng nh cng tt.
V d nh lng HCl vi NaOH cho im tng ng pH = 7 nhng ch th
c dng l phenolphtalein li chuyn mu pH = 9 nn trong trng hp ny
thng kt thc nh lng sau im tng ng gy nn sai s do ch th gy ra.
3.2. Phn loi cc phng php phn tch th tch
C 2 cch phn loi phng php:
- Da vo c ch phn ng.
- Da vo thao tc chun .
3.2.1. Phn loi phng php th tch theo c ch phn ng:
a. Chun trung ha (phng php trung ha) da vo cc phn ng trung ha
ca Bronsted
Axit
1
+ Baz 2 Baz 1 + Axit 2
Hoc n gin:

18
H
+
+ OH
-
= H
2
O
H
3
O
+
+ OH
-
2H
2
O
(n s ion H
+
, OH
-
tham gia phn ng)
b. Chun xy ha kh (phng php xy kh)
a' Kh
1
+ bOx
2
aOx
1
+ bKh
2

Cc bn phn ng:
aOx
1
+ ne = aKh
1
E
o
Ox1/Kh1
bOx
2
+ me = bKh
2
E
o
Ox2/Kh2


n
M
= (n: s in t trao i trong bn phn ng)
c. Chun kt ta (phng php kt ta): Da vo phn ng to kt ta:
M
n+
+ nX
-
= MXn + T
MXn


n
M
= ( n s ion M
n+
tham gia phn ng)
d. Chun to phc (phng php to phc hay phng php Complexon).
Da vo phn ng to phc cht ca cc ion kim loi vi dung dch tiu
chun l cc complexon (EDTA).

2 2
ionKL EDTA
M M
= =
3.2.2. Phn loi theo thao tc chun :
Gm 2 nhm
- Chun trc tip
- Chun gin tip
a. Chun trc tip:
Cht cn phn tch c chun trc tip bng dung dch tiu chun, vic xc
nh ny trnh c sai s cho php chun .
V d: phng php trung ha : Xc nh HCl bng NaOH
Phng php kt ta : Xc nh Cl
-
bng phng php Mohr
b. Chun gin tip:
Trong trng hp cht cn phn tch khng phn ng c trc tip vi dung
dch tiu chun, hoc tc phn ng gia thuc th v cht cn xc nh nh, d
tc dng CO
2
, H
2
O ca khng kh, khng chn c ch th, khng pht hin c
im tng ng phi chun gin tip c chia 2 cch:
- Cch chun ngc (chun d):

19
L php chun trong ngi ta cho cht cn xc nh A tc dng vi
mt lng d dung dch tiu chun B sau chun lng d ca B bng dung
dch tiu chun C.
V d: Chun Cl
-
bng dung dch tiu chun AgNO
3
vi mt lng d
chnh xc, lng d AgNO
3
c chun bng dung dch tiu chun KSCN.
- Cch chun th:
V d: Xc nh Cu
2+
bng phng php Iod Thiosunfat
2Cu
2+
+ 4I
-
= 2CuI + I
2

I
2
+ 2Na
2
S
2
O
2
= 2NaI + Na
2
S
4
O
6

3.3. Yu cu i vi phn ng dng trong phng php phn tch th tch:
Trong phng php phn tch th tch v thi gian chun ngn, khng cho
php d thuc th nn phn ng ha hc c dng phi tha mn cc yu cu sau.
1. Phn ng phi xy ra hon ton: Ngha l phn cht cn phn tch cha tham
gia phn ng phi nh hn sai s cho php (sai s 0,1%, 1%. . . )
Mun nh vy hng s cn bng phi ln nm trong khong K > 10
6

phn ng xy ra hon ton.
Khi phn ng khng hon ton phi c bin php thc y phn ng xy ra
hon ton nh dng phn ng ph hay dng h m.
2. Phn ng ch cho mt loi sn phm duy nht: C nh vy mi xc nh
c ng lng gam, hoc lng tiu tn thc ca cc cht tham gia phn
ng. Cc phn ng ph xy ra khng c nh hng n phn ng chun
.
V d: dung dch tiu chun KMnO
4
thng dn n ion Cl
-
s nh hng n
qu trnh chun .
Bi v trong cc phn ng xy ha - kh thng c km theo cc phn ng ph.
3. Phn ng phi c tnh chn lc cao: trnh s nh hng ca cc ion gy
nhiu, nu c phi tm cch tch cho cc ion khng gy nhiu.
4. Tc phn ng phi ln: Tc khng tn ti trng thi d thuc th ti
im tng ng.
Trong thc t nhiu phn ng nh phn ng to kt ta, phn ng xy ha
kh tc phn ng chm cn phi tng tc phn ng bng xc tc, nhit .
. .
5. Phn ng phi c cht ch th thch hp xc nh im tng ng.
3.4. Cch pha dung dch tiu chun
3.4.1. Nguyn tc pha

20
Khi pha dung dch tiu chun phi tun theo cc nguyn tc sau:
a. Xc nh dung dch tiu chun cn pha s dng cho phng php
chun no, trong mi trng no xc nh ng lng gam
ca cht ca cht cn pha.
V d: khi pha dung dch KMnO
4
cn phi xc nh ng lng trong tng mi
trng khc nhau.
Trong mi trng axit:
MnO
4
-
+ 5e + 8H
+
Mn
2+
+ 4H
2
O

5
M
=

Trong mi trng trung tnh:
MnO
4
-
+ 3e + 2H
2
O MnO
2
+ 4OH
-


3
M
=

Trong mi trng baz:
MnO
4
-
+ 1e = MnO
4
2-
1
M
=

b. Xc nh nng v th tch cn pha l bao nhiu t tnh ra s
gam ca cht cn pha.
V d: Pha 2 lt dung dch tiu chun KMnO
4
0,1N chun trong mi
trng axit

6 , 31
5
158
5
= = =
M

Vy khi lng cn pha thnh 2 lt dung dch l:
a = . N. V = 31,6 x 0,1x2 = 6,3g
3.4.2 Cch pha
Gm 2 cch:
3.4.2.1. Pha trc tip t cht gc:
Cc cht tha mn cc iu kin sau c gi l cht gc:
* Cht phi tinh khit v phng din ho hc, lng tp cht khng qu 0,1% nu
qu phi tinh ch li.
* Phi c thnh phn ng ng vi cng thc ha hc, k c nc kt tinh.

21
* Phi bn v phng din ha hc trng thi rn cng nh trng thi dung dch :
khng b phn hy di tc dng ca nh sng, nhit thng khng phn ng
vi kh CO
2
, hi nc, xy khng kh, khng qu nhy vi cc cht xy ha kh.
* ng lng gam cng ln cng tt gim sai s cn.
V d: cc cht gc: K
2
Cr
2
O
7
, H
2
C
2
O
4
.2H
2
O, Na
2
B
4
O
7
.10H
2
O. . . cc cht
khng phi cht gc: NaOH d ht m, phn ng vi CO
2
khng kh to ra Na
2
CO
3
,
NH
4
OH d bay hi, HCl d bay hi, KMnO
4
d phn hu di tc dng nh sng. .
.
Cch iu ch: cn mt lng chnh xc trn cn phn tch c sai s + 0,2mg
ha tan vo bnh nh mc v cho thm nc n vch.
Cn a gam cht gc ha tan thnh Vml dung dch, c ng lng gam l vy
nng ca dung dch l:
3
10
.
=
D V
a
N

3.4.2.2. Pha gin tip: c hai cc pha
Cch 1:
Pha dung dch c nng gn ng vi nng cn pha, ri dng dung dch
c nng chnh xc t cht gc xc nh li nng dung dch va pha.
V d: Khi pha 1 lt dung dch NaOH 0,1N s gam cn pha l: a = 1. 0,1.40 =
4 gam
Ngi ta cn 4g NaOH ha tan vo thnh 1 lt dung dch. Ri dng dung
dch tiu chun H
2
C
2
O
4
.2H
2
O 0,1N xc nh li nng dung dch va pha.
Cch 2:
Pha dung dch vi nng gn ng vi nng cn pha (thng ln hn)
ri xc nh li bng dung dch tiu chun t cht gc ri t tnh c lng
nc cn pha thm c nng chnh xc cn pha theo biu thc (3.1):

) ( ' 1
'
2
ml V
N
N
V
O H
|
.
|

\
|
=
(3.1)

N: Nng pha.
N : Nng cn pha chnh xc.
V: Th tch dung dch pha cn li cn pha long.
T tnh c lng V
H2O
cn pha cho c dung dch c nng chnh
xc. Ngoi ra ngi ta cn iu ch bng ng chun (Fixanal) tc l ng c ng
mt lng chnh xc cc cht, ch cn ha tan mt th tch chnh xc c ghi
sn trong nhn s c nng chnh xc c pha.

22
3.5. Cc loi nng v cch tnh kt qu
3.5.1 Cc loi nng
3.5.1.1. Nng th tch: Nng th tch ca mt cht lng l t s gia th
tch cht lng v th tch ca dung mi.
V d: HCl 1:4 gm 1 th tch dung dch HCl v 4 th tch nc.
3.5.1.2. Nng %: l s gam ca cht tan c trong 100 gam dung dch.
Nu a l s gam cht tan , b l s gam dung mi ta c.

100 %
+
=
b a
a
C
(3.2)
Nu a l cht lng c Vml dung dch, c khi lng ring l d.


100
.
% =
d V
a
C
(3.3)
3.5.1.3. Nng phn t gam ( M,ptg/l, mol/l): S phn t cht tan c trong 1
lt dung dch.
Nu a l s gam cht tan, trong Vml dung dch, c M l phn t gam cht tan ta
c.

3
10
.
=
M V
a
N
(3.4)
3.5.1.4. Nng ng lng gam ( N ): S ng lng gam cht tan c
trong mt lt dung dch
Nu a l s gam cht tan, trong Vml dung dch, c ng lng gam l .

3
10
.
=
D V
a
N
(3.5)
- ng lng gam: ca mt cht l lng cht m khi lng tnh ra
gam ca n c tr s bng khi lng ca ng lng ( tnh theo n v carbon).
V d: * 1 ng lng hydro cn nng 1,00797vC
V 1 ng lng HCl cn nng 36,461vC
* Mili ng lng gam l 1/1000 ng lng gam
- ng lng gam ca mt cht khng phi l mt hng s m n thay i
theo phn ng m n tham gia, trong nhiu trng hp, c th tnh ng lng
gam ca mt cht da theo cng thc:
= M/n
Trong : = ng lng gam

23
M = phn t lng
n = S ion H
+
m mt phn t axit ( hay baz) cho (hay nhn) trong
phn ng trung ho; s ho tr ca mt phn t tham gia phn ng trao i; s in
t do mt phn t trao i trong phn ng xy ho- kh.
V d: H
2
SO
4
+ 2H
2
O = Na
2
SO
4
+ 2H
2
O
H2SO4
= M/2
Ba(OH)
2
+ 2HCl = BaCl
2
+ 2H
2
O
Ba(OH)2
= M/2
3. 5.1.5. chun theo cht cn xc nh T
A/ B

chun ca thuc th B theo cht cn xc nh A l s gam ca cht cn xc
nh A tc dng va vi 1ml dung dch tiu chun B.
V d: T
AgNO3/Cl-
= 0,0120 tc l 1ml dung dch tiu chun AgNO
3
s tc dng
c 0,0120gam ion Cl
-
.
T
KMnO4/Fe2+
= 5,620mg/ml tc l 1ml KMnO
4
xy ho c 5,620mgFe
2+

Cch biu din nng ny thun tin cho vic tnh ton kt qu, khi cn phn
tch nhiu mu trong thc t sn xut.
chun T
A/B
c xc dnh theo biu thc:

3
B
A
10
D
.D
=
a
T
AB
(3.6)

a: lng cn cht B tnh bng gam

A
;
B
: ng lng gam ca A v B
V d1: - Pha dung dch T
AgNO3/ Cl
-
= 0,00355 th lng cn em pha l:
a = 16,9875g
V d 2: Tnh chun ca KMnO
4
theo st, bit rng khi chun dung dch
cha 0,1170g Fe
2+
th tn ht 20ml dung dch KMnO
4
.
T
KMnO4
= 0,1170 / 20 = 0,00585g/ml hay 5,58mg/ml
V d 3: chun ca KMnO
4
theo st bng bao nhiu, nu ho tan 3,1610g
KMnO
4
thnh 1t dung dch.
5Fe
2+
+ MnO
4
-
+ 8H
+
= Mn
2+
+ 5Fe
3+
+ 4H
2
O
T
KMnO4/Fe2+
= 3,161.55,85/ 31,61 .10
3
= 0,005585g/ml
3.5.2 Cch tnh kt qu trong phn tch th tch
Vic tnh kt qu trong phn tch th tch da vo th tch dung dch tiu
chun tiu tn, lng cn mu ban u. V cch tnh da vo nh lut ng
lng.
3.5.2.1 nh lut ng lng

24
* nh lut c pht biu: Cc cht tc dng vi nhau theo nhng phn trng
lng t l vi ng lng ca chng.
C phn ng tng qut sau:
mA + nB = pC + qD
Cc cht tham gia phn ng vi khi lng l m
A
; ng lng
A
v m
B
;
ng lng l
B
, ta c:
B
A
D
D
=
B
A
m
m

Hay:
B A
D D
B A
m m
=

Vy: A
D
A
m
: S ng lng cht A.
B
D
B
m
: S ng lng cht B
Nh vy nh lut c pht biu: Cc cht phn ng vi s ng lng
bng nhau.
* H qu ca nh lut:

- N
A
. V
A
= N
B
. V
B
(3.7)
Nu cn ag cht tinh khit( thng l cht gc) ho tan thnh dung dch ri
chun ht V
B
ml dung dch tiu chun B c nng N
B

-
B B
V N
a
. 10 .
D
3
A
=

(3.8)
3.5.2.2 Tnh kt qu theo chun trc tip:
Cn a gam cht cn xc nh A ho tan thnh dung dch, ly V
A
ml cht cn
xc nh A chun ht V
B
ml dung dch tiu chun B c nng N
B
.
*Nng cht cn xc nh A l:
=
A
N
A
B B
V
N V .
(3.9)
*S gam cht cn xc nh A l:
- =
A
m
A
D
1000
.
B B
N V
(3.10)

25
*Hm lng %A c trong a gam mu ban u l:
- =
A
%
A
D
1000
.
B B
N V
(3.11)
3.5.2.3 Tnh kt qu theo chun ngc( hoc d)
Chun ny p dng trong trng hp khng th thc hin chun trc
tip. Ngi ta cn a gam cht cn xc nh A. Ho tan thnh dung dch, ly V
A
ml
dung dch A cho tc dng mt lng d chnh xc V
B
ml dung dch tiu chun B c
nng N
B
. Chun lng d dung dch tiu chun B bng dung dch tiu chun
C c nng N
C
, ht th tch V
C
ml.
Cc phn ng xy ra trong php chun :
A + B = P (1)
B + C = Q (2)
- Nng ca cht cn xc nh A l:
=
A
N
A
C C B B
V
N V N V . .
(3.12)
- S gam cht cn xc nh A l:
=
A
m
A
D
1000
. .
C C B B
N V N V
(3.13)
- Thnh phn % ca A c trong a gam mu l:

A
N V N V
A
C C B B
100
. D
1000
. .
%
A

= (3.14)
Mt s bi tp p dng












26
Chng 4:
PHN NG TRAO I PROTON.
PHNG PHP CHUN AXIT - BAZ
4.1. Mt s khi nim c bn:
4.1.1. nh ngha axit - baz theo Bronsted:
Theo quan im axit - baz ca Bronsted: axit l nhng cht c kh nng cho
proton, baz l nhng cht c kh nng nhn proton.
Mt axit sau khi cho mt proton th tr thnh mt baz gi l baz lin hp
vi axit c gi l mt cp axit - baz lin hp.
Axit (A) baz (B) + H
+

Proton khng tn ti t do, mun cho mt axit nhng proton th phi c mt
baz c kh nng nhn proton. Qu trnh trao i proton gia axit v baz to thnh
mt baz mi v axit mi gi l phn ng trung ho.
Axit 1 + baz 2 baz 1 + axit 2
Axit v baz c th l nhng axit mnh, baz mnh hoc yu tu thuc vo
bn cht ca axit, baz l dung mi m n ho tan.
V d:
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+

Axit Baz
CH
3
COOH + H
2
F
2
CH
3
COOH
2
+
+ HF
2
-

Baz Axit
4.1.2. Nc v pH:
Nc l mt dung mi c th cho hoc nhn proton
2H
2
O H
3
O
+
+ OH
-

(H
3
O
+
l pronton hirat ho gi l hironi hoc oxoni thng vit n gin H
+
)
p dng nh lut tc dng khi lng ta c:

| || |
| |
| | | || |
n
K OH O H O H K
O H
OH O H
K
= =
=
+
+
. .
.
3
2
2
2
2
3

c gi l tch s ion ca nc, 25C:
14
10

=
n
K
Trong nc nguyn cht: | | | | l mol OH O H / 10
7
3
+
= =
Thng biu din axit ca mt dung dch:

27
| |
+
= O H pH
3
. lg ch s hir
| |

= OH pH . lg ch s hirxyl
7 = pH mi trng trung tnh, 7 > pH mi trng baz, 7 < pH mi trng
axit.
4.1.3. Cng ca axit v baz. Hng s cp axit - baz:
Xt dung dch trong nc ca axit A ta c:
A + H
2
O B + H
3
O
+


| || |
| || |
| |
| || |
| | A
O H B
O H K K
O H A
O H B
K
A
+
+
= =
=
3
2
2
3
.
.
.
.
| | O H
2
coi khng i
K
A
c gi l hng s axit ca axit A v biu th cng ca axit A v K
A

cng ln, axit phn ly cng nhiu, axit cng mnh.
Xt dung dch trong nc ca baz B ta c:
B + H
2
O A + OH
-


| || |
| || |
| |
| || |
| | B
OH A
O H K K
O H B
OH A
K
B

= =
=
.
.
.
.
2
2

K
B
c gi l hng s baz ca baz B, biu th cng ca baz B v K
B

cng ln, baz phn ly cng mnh.
Khi axit A v baz B l cp axit - baz lin hp
B
A
th

| || || || |
| || |
| || |
14
3
3
10 . .
.
. . .
.
+
+
= = =
=
n B A
B A
K OH O H K K
B A
OH A O H B
K K

thun tin cho vic tnh ton ngi ta thng dng:

14 . .
. lg .
. lg .
= +
=
=
B A
B B
A A
K p K p
K K p
K K p

4.1.4. Cng thc tng qut tnh | |
+
O H
3
ca cp axit - baz lin hp:

28
Xt dung dch gm axit HA c nng C
A
, v NaA c nng C
B
tc l ta
c cp axit - baz lin hp

A
HA
, cho K
A.

Trong dung dch c cc cn bng sau:
NaA = Na
+
+ A
-
(1)
HA + H
2
O A
-
+ H
3
O
+
(2)
2H
2
O H
3
O
+
+ OH
-
(3)
Nh vy trong dung dch s c mt 5 cu t: HA, A
-
, Na
+
, H
3
O
+
, OH
-

Ta c:

| | | |
| | HA
A O H
K
A
+
=
3
(1)
| | | |
+
= OH O H K
n 3
(2)
Phng trnh bo ton khi lng:
| |
B
C Na =
+
(3)
| | | |
B A
C C A HA + = + (4)
Phng trnh trung ho in:
| | | | | | | |
+ +
+ = + A OH Na O H
3
(5)
T 5 phng trnh trn gii ra ta c:
| |
| | | |
| | | |
+
+
+
+
+
=
OH O H C
OH O H C
K O H
B
A
A
3
3
3
. (4.1)
y l cng thc tng qut tnh | |
+
O H
3
trong dung dch nc ca mt cp
axit - baz lin hp.
4.2. Phng php nh lng axit - baz:
4.2.1. Nguyn tc:
Phng php chun axit - baz l phng php nh lng ho hc da
trn phn ng trung ho:
Axit 1 + baz 2 = baz 1 + axit 2
Trong qu trnh chun pH dung dch bin i, pht hin im tng
ng ngi ta phi cho thm cht ch th mu, cht ch th i mu s l dng qu
trnh chun , v mun chn c ch th phi xy dng ng cong chun .
4.2.2. ng cong chun trong phng php trung ho.

29
4.2.2.1. ng cong chun axit mnh bng baz mnh.
V d: Xy dng ng cong chun v chn ch th thch hp khi chun
V
HA
trong dung dch axit mnh HA c nng N
HA
bng dung dch baz mnh
BOH c th tch V
BOH
v nng N
BOH
.
Phn ng chun :
HA +BOH = AB + H
2
O
H
+
+ OH
-
= H
2
O
Xc nh pH dung dch cc thi im
Khi cha chun : Trong dung dch ch c axit mnh HA, axit ny phn ly
hon ton trong dung dch .
HA = H
+
+ A
-


| |
| |
HA
N H
H pH
=
=
+
+
lg

Vy
HA
N pH lg =
Ln cn trc im tng ng: Thi im cho thiu 0,1% BOH vo dung
dch, trong dung dch phn ng chun xy ra, lm gim nng HA v
nng axit cn li s quyt nh pH ca dung dch:

BOH HA
BOH BOH HA HA
BOH HA
BOH BOH HA HA
HA
V V
N V N V
pH
V V
N V N V
C
+

=
+

=
. .
lg
. .
(4.2)
Ti im tng ng: Ton b lng HA c trung ho ht hay phn
ng chun trng thi cn bng, trong dung dch ch c mui AB v
H
2
O. Mi trng trung tnh:
7 =
T
pH
Ln cn sau im tng ng: Thi im cho d 0,1% BOH vo dung dch,
pH dung dch do lng d BOH quyt nh, BOH l dung dch baz mnh
nn phn ly hon ton:
BOH = B
+
+ OH
-


HA BOH
HA HA BOH BOH
HA BOH
HA HA BOH BOH
BOH
V V
N V N V
pOH pH
V V
N V N V
C
+

+ = =
+

=
. .
lg 14 14
. .
(4.3)
ng cong chun axit mnh, baz mnh c dng.

30


Nhn xt:
- Trc v sau ln cn im tng ng, pH dung dch thay i t t.
- Khi cho thiu 0,1%, d 0,1% (ln cn im tng ng) pH dung dch thay i
mt cch t ngt, to nn bc nhy chun .
- pH
T
trng vi im trung tnh, 7 = pH
- ng vi sai s cho trc ( %... 1 %, 1 , 0 ) s c mt bc nhy tng ng trn
ng cong, sai s ln bc nhy chun di.
- Bc nhy chun cn ph thuc vo nng cc cht tham gia phn ng
chun , dung dch tiu chun c nng cng ln bc nhy chun di.

31
4.2.2.2. ng cong chun axit yu bng baz mnh.
V d: Xy dng ng cong chun v chn ch th thch hp khi chun axit
yu HA c nng N
HA
, th tch V
HA
bng dung dch baz mnh BOH c th tch
V
BOH
, nng N
BOH
. Cho gi tr pK
a
.
Phn ng chun :
HA + BOH AB + H
2
O
Khi cha chun trong dung dch ch c axit yu HA phn ly:
HA + H
2
O H
3
O
+
+ A
-

Theo cng thc tnh | |
+
O H
3
trong dung dch nc ca mt cp axit - baz lin
hp: (4.1)
| |
| | | |
| | | |
+
+
+
+
+
=
OH O H C
OH O H C
K O H
BOH
HA
a
3
3
3
. (*)
Do | |

OH rt nh khng ng k, axit in ly yu | |
+
>> O H C
HA 3
v 0 =
BOH
C thay
vo biu thc (4.1) ta c:
| |
| |
+
+
=
O H
C
K O H
HA
a
3
3
.
Hay:

| |
| |
HA a
HA a
C K O H
C K O H
lg
2
1
lg
2
1
lg
.
3
3
=
=
+
+


HA a
C K p pH lg
2
1
.
2
1
= (4.4)
Cng thc tnh pH ca dung dch axit yu
Vy:
HA a
N K p pH lg
2
1
.
2
1
= (4.5)
Ln cn trc im tng ng thiu 0,1% BOH: trong dung dch tn ti
cp axit - baz lin hp (dung dch m

A
HA
; do HA cn d trong dung
dch v mui in ly) vy ta c:
| | | |
+
>> >> OH C O H C
BOH HA
;
3

Thay vo biu thc (4.1) c:
| |
BOH
HA
a
C
C
K O H .
3
=
+
hay
BOH
HA
a
C
C
K p pH lg . = (4.6)

32
Ta c
BOH HA
BOH BOH HA HA
HA
V V
N V N V
C
+

=
. .

BOH HA
BOH BOH
BOH
V V
N V
C
+
=
.

Thay vo (4.3) ta c:
BOH BOH
BOH BOH HA HA
a
N V
N V N V
K p pH
.
. .
lg .

= (4.7)
Ti im tng ng: cho 100% lng BOH vo dung dch, trong dung
dch ch c mui AB v nc, y l mui ca axit yu v baz mnh nn
trong dung dch thu phn cho mi trng baz. Vy | |

>> OH C
BOH
;
0 =
HA
C ; | |
+
O H
3
khng ng k.
Thay vo (4.1) c:
| |
| |
BOH
a
C
OH
K O H

+
= .
3
M | |
| |
+

=
O H
OH
3
14
10

Vy: | |
| |
BOH
a
C O H
K O H
+

+
=
3
14
3
10
.
Hay: | |
BOH
a
C
K O H
14
2
3
10
.

+
= hay | |
BOH
a
C
K O H
14
3
10
.

+
=
| |
BOH a
C pK O H lg
2
1
10 lg
2
1
2
1
lg
14
3
+ =
+


BOH a T
C pK pH lg
2
1
7
2
1
+ + = (4.8)
Cng thc tnh pH ca mt baz yu.
Mt cch gn ng:

BOH HA
HA HA
BOH
V V
N V
C
+
=
.


BOH HA
HA HA
a T
V V
N V
pK pH
+
+ + =
.
lg
2
1
7
2
1
(4.9)
Ln cn sau im tng ng: d 0,1% BOH vo dung dch, lng d
BOH quyt nh pH dung dch, y l baz mnh. Vy pH dung dch c
tnh (4.3):

HA BOH
HA HA BOH BOH
V V
N V N V
pH
+
+
+ =
. .
lg 14
ng cong chun axit yu bng baz mnh c dng:

33


Nhn xt:
- ng cong chun l ng cong bt i xng, im tng ng nm lch
mi trng kim.
- Bc nhy chun ngn: chn ch th Phnolphtalein.
- Bc nhy chun ph thuc:
+ Sai s php chun : sai s ln bc nhy chun di.
+ Nng cc cht tham gia phn ng: nng ln bc nhy chun di.
+ Hng s cn bng ca axit K
a
nu K
a
qu nh khng c bc nhy chun
, khng chn c ch th mu.

34
4.2.2.3. ng cong chun baz yu bng axit mnh.
V d: Xy dng ng cong chun khi chun baz yu BOH c V
BOH
, N
BOH

bng axit mnh HA c V
HA
, N
HA
, cho pK
b
ca baz.
Phn ng chun :
BOH + HA AB + H
2
O
Khi cha chun : trong dung dch ch c baz yu BOH, baz yu BOH s
quyt nh pH ca dung dch theo biu thc. (4.8)

BOH a
C pK pH lg
2
1
7
2
1
+ + =
Ta c
b
pK pH =14 thay vo c:

BOH b
C pK pH lg
2
1
2
1
14 + = (4.10)
Thay
BOH BOH
N C = ta c:

BOH b
N pK pH lg
2
1
2
1
14 + =
Ln cn trc im tng ng: cho thiu 0,1% HA vo dung dch, lng
d baz yu v mui to h dung dch axit - baz lin hp (dung dch m)
+
B
BOH


| | | |
| |
BOH
HA
a
BOH
HA
a
BOH HA
C
C
pK pH
C
C
K O H
OH C O H C
lg .
;
3
3
= =
>> >>
+
+

Ta c:
b a
pK pK =14 thay vo ta c:

BOH
HA
b a
C
C
pK pK lg 14 =
Tng t t s:
HA HA BOH BOH
HA HA
BOH
HA
N V N V
N V
C
C
. .
.

=

HA HA BOH BOH
HA HA
b
N V N V
N V
pK pH
. .
.
lg 14

= (4.11)
Ti im tng ng: cho 100% HA vo dung dch, do phn ng t trng
thi cn bng, trong dung dch ch c mui AB, mui baz yu, axit mnh
thu phn cho mi trng axit

HA a
C pK pH lg
2
1
2
1
=
Ta c:

b a
pK pK =14

35
Vy

HA b
C pK pH lg
2
1
2
1
7 =

HA BOH
BOH BOH
b
N V
N V
pK pH
+
=
.
lg
2
1
2
1
7 (4.12)
Ln cn sau im tng ng: cho d 0,1% HA vo dung dch, lng d
axit mnh HA quyt nh pH dung dch theo (4.2) ta c:

BOH HA
BOH BOH HA HA
V V
N V N V
pH
+

=
. .
lg
ng biu din chun baz yu bng axit mnh c dng:


Nhn xt:
- y l dng ng cong bt i xng, im tng ng nm lch mi trng
axit
- Bc nhy chun ph thuc:
+ Sai s
+ Nng cc cht tham gia yu
+ K
b
qu nh khng c bc nhy chun
4.2.2.4. ng cong chun axit a chc v baz a chc:
1. iu kin nh phn axit a chc (hn hp cc axit)
baz a chc (hn hp cc baz)

36
V d: Gi s c 2 axit HA
1
, HA
2
c nng C, vi hng s phn ly K
1
, K
2

c chun bng NaOH. Hy tm iu kin nh phn hai axit vi sai s php
chun khng qu 1%.
Khi nh hng c cc phn ng:
HA
1
+ NaOH = NaA
1
+ H
2
O (1) pK
1

HA
2
+ NaOH = NaA
2
+ H
2
O (2) pK
2

V K
1
>K
2
nn lc u ch c phn ng (1) xy ra, cn (2) coi nh khng xy ra,
nhng v sau c hai phn ng xy ra ng thi, nn pH ca dung dch phi l kt
qu ca 2 phn ng (1)(2):

| |
| |
| |
| |

= =
2
2
2
1
1
1
lg lg
A
HA
pK
A
HA
pK pH

| |
| |
| |
| |

=
2
2
1
1
2 1
lg lg
A
HA
A
HA
pK pK (4.13)
Mun sai s chun khng qu 1%, th: | | C A % 99
1
=

, | | C HA % 1
1
=

;
| | C A % 1
2
=

, | | C HA % 99
2
=

.
Thay vo biu thc (4.13) c 4
2 1
~ pK pK
Hay
4
2
1
10 >
K
K

Vy nh phn mt axit a chc hay hn hp axit, sai s php chun
khng qu 1% axit phi c
4
2
1
10 >
K
K
. . .
2. ng cong chun axit a chc:
V d: Xy dng ng cong chun v chn ch th thch hp khi chun
20ml H
3
PO
4
0,1N bng NaOH 0,1N.
Ta c:
H
3
PO
4
H
+
+ H
2
PO
4
-
pK
1
=2,13
H
2
PO
4
-
H
+
+ HPO
4
2-
pK
2
=7,21
HPO
4
2-
H
+
+ PO
4
3-
pK
3
=12,32
Khi cha chun : do H
3
PO
4
l mt axit yu nn pH dung dch c tnh
theo chc axit th nht, nhng chc axit sau c lc qu nh c th b qua :
615 , 1 1 , 0 lg
2
1
23 , 2 .
2
1
lg
2
1
2
1
= = =
HA a
C pK pH
T khi chun n im tng ng 1 trong dung dch ch c mui
NaH
2
PO
4
, y l cht lng tnh nn pH c xc nh:
( ) ( ) 66 , 4 21 , 7 12 , 2
2
1
2
1
2 1
= + = + = pK pK pH

37
Ti im tng ng 2 trong dung dch Na
2
HPO
4
, y cng l mt cht
lng tnh nn pH dung dch c tnh:
( ) ( ) 79 , 9 38 , 12 21 , 7
2
1
2
1
3 2
= + = + = pK pK pH
Ti im tng ng 3 dung dch ch cha Na
3
PO
4
mui ca axit yu, baz
mnh nn khi thu phn cho mi trng baz yu:
71 , 12 lg
2
1
2
1
7
3
= + + =
BOH
C pK pH
ng cong chun axit a chc bng baz mnh c dng:

Nhn xt:
- Trong php chun c 3 im tng ng :
+ im tng ng 1: Chn ch th metyl
+ im tng ng 2: Chn ch th phenolphtalein
+ im tng ng 3: Khng c bc nhy chun , khng chn c
cht ch th mu.
- Nh vy vi hn hp axit, baz phi c
4
2
1
10 >
K
K
mi c bc nhy chun
mi chn c ch th mu.
4.2.3. Cht ch th trong phng php axit - baz:
4.2.3.1. Khi nim:
Ch th trong phng php axit - baz l axit, baz hu c yu c mu dng
phn t khc mi dng ion, khi c s bin i v pH, lm cho cu trc phn t bin
i, dn n mu sc thay i.
HInd + H
2
O Ind
-
+ H
3
O
+


38
Dng axit (HInd) c mu khc dng baz (Ind
-
) lin hp
V d: Metyl da cam

4.2.3.2. Khong pH chuyn mu ca ch th:
Theo (4.13) ta c hng s cn bng theo nh lut tc dng khi lng:

| | | |
| | HInd
Ind O H
K
HInd
+
=
3
hay | |
| |
| |

+
=
Ind
HInd
K O H
HInd
.
3

Mu ch th bin i khi n chim
10
1
so tng lng cht ban u:

| |
| | HInd
Ind
pK pH
HInd

+ = (4.14)
| | | | HInd Ind
10
1
>

thy mu dng Ind

-
thay vo (4.13) ta c:
1 =
HInd
pK pH (4.15)
4.2.3.3. Yu cu chung i vi ch th:
- D tan (trong nc hoc cn).
- Nng 10
-4
- 10
-5
M phi xut hin mu r.
- pH chuyn mu ca ch th nm trong bc nhy chun .
- Bn trong iu kin thng.
Bng 4.1 Mt s ch th thng dng
Mu
Ch th
Axit Baz
Khong pH
chuyn mu
pT
Metyl da cam vng 3,4 - 4,4 4
Metyl vng 4,4 - 6,4 5
PP khng mu Tm hng 6,4 - 10,4 9



39
CHNG 5
PHN NG KT TA
PHNG PHP CHUN KT TA.

5.1. S to thnh kt ta v quy lut tch s tan:
Khi ho tan mt cht no trong nc, th hai qu trnh ngc chiu nhau
s xy ra cng mt lc.
Khi dung dch ca cht no cha bo ho, th qu trnh ho tan nhng
lng mi ca cht s ln hn qu trnh kt ta n t dung dch.
V d: AB ho tan A
+
+ B
-

Ta kt ta Dung dch
AgCl ho tan Ag
+
+ Cl
-

Ta kt ta Dung dch
Khi dung dch qu bo ho, c hin tng ngc li qu trnh tch cht tan
khi dung dch ln hn qu trnh ho tan n.
Khi dung dch bo ho c kt ta cht tan lng xung di, trng thi cn
bng ng c thit lp. Trong trng hp ny tc ho tan bng tc kt ta.
Khi cn bng c thit lp, trong 1 n v thi gian c bao nhiu ion Ag
+
v
Cl
-
chuyn thnh kt ta, cng c by nhiu ion chuyn t b mt kt ta vo
dung dch.
Theo nh lut tc dng khi lng khi cn bng c thit lp, trong dung
dch nc bo ho ta c:
| | | |
| | AgCl
Cl Ag
K
+

=
AgCl

Trong cc h ng th, s va chm gia cc phn t c bn xy ra trong ton
b vt th ca cht. Trong cc h d th, s va chm gia cc phn t c bn ca
cht tan v cht rn ch xy ra trn b mt phn chia cc tng v khng ph thuc
vo lng ca cht rn, nng ca n khng i v khng nh hng n tc
ca phn ng. Do c th vit:
[Ag
+
] x [Cl
-
] = K
AgCl
x [AgCl] = hng s
Tch s nng cc ion ca cht in ly t tan trong dung dch nc bo ho
gi l tch s tan v c k hiu bng ch T cng vi cng thc ho hc ca cht
in ly .
V d: [Ag
+
] x [Cl
-
] = T
AgCl

[A
n+
]
m
x [B
m-
]
n
=
n
B
m
A
T =hng s

40
ng hn: | | | |
n
B
m
A
A
- m n
A
a a T , B A T
n
m
+
= =
+
m
n n m
B
n m
B
(5.1)

n
B
m
A
a , a
n + m
:hot ca ion A
n+
, B
m-

ngha trong phn tch:
Theo nh lut tc dng khi lng khi thit lp cn bng trong dung dch
nc bo ho ca cht in ly t tan nhit v p sut nht nh, tch s nng
ion (T) l i lng khng i v c biu din bng cng thc chung:
T
AmBn
= hng s (const) = [A]
m
x [B]
n
h s m, n ch s ion tng ng to thnh khi phn ly 1 phn t.
- Nu tch s [A]
m
x [B]
n
> T
AmBn
th hp cht t tan tch ra dng kt ta (mun
c kt ta).
- Nu tch s [A]
m
x [B]
n
< T
AmBn
kt ta khng tch ra m b ho tan (mun kt
ta tan c).
Quy lut ny l c s l thuyt quan trng lm c s ca l thuyt to thnh kt
ta. N c ngha trong phn tch l bit T ca mt cht ta c th suy ra iu kin
c kt ta hay ho tan ta.
Thm bt k ion to thnh hp cht A
m
B
n
u lm gim tan, thm cc cht
in ly khc khng c ion chung vi hp cht A
m
B
n
lm tng tan.
5.2. Quan h gia tan v tch s tan.
c trng cho tnh tan ca kt ta, ngoi T, ngi ta cn dng tan S. tan
S v T lin quan mt thit vi nhau, bit T c th tnh c tan v ngc li.
tan tnh theo mol/l, g/l.
- i vi cht in ly t tan dng AB (cng ho tr), th d AgCl, Ba SO
4
.
AB A
+
+

B
-

| | | |
AB
-
T B A = = =
+
AB
S
| | | |
-
AB
B A T =
+

Th d: Tnh tan ca BaSO
4
, bit
11
BaSO
10 9 , 9 T
4

=
5 11
BaSO BaSO
10 10 9 , 9 T
4 4

~ = = S (mol/l)
-
i vi cht in ly t tan dng A
m
B
n
(khng cng ho tr), th d Ag
2
CrO
4
A
m
B
n
mA
n+
+ nB
m-

n m
n m
B
n m
S
n
+
=
m
A
T
(5.2)

41
Th d: Tnh tan ca Ca
3
(PO
4
)
2
20 25
0
C trong nc nguyn cht. bit
33
) ( Ca
10 16 , 3 T
2 4 3

=
PO

Ca
3
(PO
4
)
2
3Ca
2+
+ 2PO
4
3-

7
5
-33
2 3
2 3
-33
10 24 , 1
108
10 3,16
2 3
10 3,16

+
=

= S (mol/l)
Tnh tan ca Ag
2
CrO
4
, bit
12
Ag
10 2 T
4 2

=
CrO

Ag
2
CrO
4
2 Ag
+
+ CrO
4
2-
4
3
-12
2 1
2 1
-12
10 79 , 0
4
10 2
2 1
10 2

+
=

= S (mol/l)

5.3. Cc yu t nh hng n tan ca kt ta.
5.3.1. nh hng ca ion chung.
Khi thm d thuc th kt ta, tan ca kt ta gim xung v ph thuc
vo lng d ca ion thm vo ng dng vi mt trong cc ion to thnh kt ta.
Th d:
- Tnh tan AgCl trong dung dch NaCl 0,1M. Bit T
AgCl
= 1,7.10
-10

| | | |
10
AB
-
10 7 , 1 T B A
+
= =
| |
| |
-
B
T
A
AB
S = =
+
d
| |
9
1
10
AgCl
10 7 , 1
10
10 7 . 1
A

+
=

= = S (mol/l)

Trong nc nguyn cht
5 10
AgCl
10 3 , 1 10 7 , 1

= = S (mol/l)
tan AgCl trong dung dch NaCl 0,1M so vi tan trong nc gim i
7647
10 7 , 1
10 3 . 1
9
5
=

ln
Nh vy, thm ion cng tn gy nh hng n tan ca cht in ly t tan
v c kh nng lm cho s kt ta tng rn hon ton hn.
Nu cho vo dung dch bo ho ca mt cht in ly t tan bt k mt mui
no khng c ion chung vi n th lc tng tc gia cc ion tng ln, do h
s hot gim xung dn n T ca cht t tan tng ln so vi i lng T ca
cht in ly ny trong nc tinh khit. S tng T ca cht in ly trong dung dch
mui bo ho ion l gy ra s tng tan ca cht in ly.

42
Tng tan ca cht in ly t tan khi c cc mui tan khc (hiu ng mui)
c gy ra do s gim h s hot gn lin vi s tng lc ion ca dung dch v
thm cc cht in ly l vo.
Ni cch khc, khng phi ch c cc cht in ly c ion chung mi nh
hng n tan ca mui t tan. tan ca mt s mui t tan tng ln khi c cc
mui tan khc khng c ion chung vi chng. Nng mui khng c ion chung
vi cht in ly t tan c thm vo cng ln th tan ca n tng ln cng nhiu,
v sc ion ca dung dch tng ln, do a cc ion khc vo, hin tng ny c gi
l hiu ng mui. S thm cc cht in ly khc nhau gy nh hng khc nhau n
tan ca cht in ly t tan v lc ion ca dung dch khng nhng ph thuc vo
nng m cn vo ln in tch ca cc ion.
V d: tan ca PbSO
4
tng ln khi c NaNO
3
, tan ca BaSO
4
, SrSO
4
,
CaSO
4
tng ln khi thm KCl, NaNO
3
, KNO
3
v.v vo dung dch.
Tnh tan ca CaSO
4
trong nc v trong dung dch NaCl 0,1M, bit
5
CaSO
10 26 , 6 T
4

=
tan trong nc:
3 5
CaSO
10 9 , 7 10 26 , 6 S
4

= = (mol/l)
tan dung dch NaCl 0,1M (I = 0,1; f
2
= 0,33)
2 5
CaSO
10 4 , 2 10 26 , 6
33 , 0
1
S
4

= =
Do tan ca CaSO
4
tronng dung dch NaCl 0,1M tng ln so vi tan
trong nc gn 3 ln 3
10 9 , 7
10 4 , 2
3
2
~

.
5.3.2. nh hng ca pH dung dch.
tan ca kt ta s tng ln khi cc ion ca kt ta tham gia phn ng vi
ion H
+
v OH
-
ca dung dch.
V d: kt ta M
m
A
n
trong A l anion ca acid y phn ng vi ion H
+

to ra HA, H
2
A.H
n
A ng vi hng s in ly K
n
, K
n-1
,. K
1
. Cn M l cation
kim loi c th to phc vi ion OH
-
:
M + OH
-
M(OH)
| |
| || |
-
1
OH M
MOH
=
M(OH) + OH
-
M(OH)
2
| |
| || |
2
-
2
2
OH M
M(OH)
=
M(OH)
p-1
+ OH
-
M(OH)
p
| |
| || |
p
p
-
p
OH M
M(OH)
=

43
( y p < m).
Do c phn ng ph nn tan tng ln. c trng cho tc ng ny
ngi ta dng khi nim tch s tan biu kin (T):
T = [M]
m
[A]
n
y [M] v [A] l tng nng ca cc dng ion v phn t ho tan
trong dung dch ca ion M v A. Trong trng hp ny:
[M] = [M] + [MOH] + [M(OH)
2
] + .+ [M(OH)
p
]
[A] = [A] + [HA] + [H
2
A] +.+ [H
2
A]
Cc h s v nh gi nh hng ca phn ng ph c tr s:
| | | | M / M'
) (
=
OH M

| | | | A / A'
) (
=
M A

| | | |
n m
T A' M ' =
| | | |
n
A(H) ) (
A . A . . M'
n
m
OH M
m
=
n
H A
m
OH M ) ( ) ( MmAn
. . T T' = (5.3)
tan ca M
m
A
n
l s th:
| | | |
n m n m
ns ms ) ( ) ( A' M' T' = = (5.4)
n m
n m
n m
T
+
=
'
S
T (5.3) v (5.4) ta c:
n m
n
H A
m
OH M n m
n m
T
+
=
) ( ) (
. . S (5.5)
Tch s
n m
. nh gi nh hng ca pH n tan s ca M
m
A
n
(so snh
cng thc). Nu trong dung dch khng c phn ng ph ca M vi OH
-
th
M
=1,
khng c phn ng ph ca A th
A
=1.
V d: Tnh tan ca calci oxalate trong dung dch c pH = 4, bit
9
10 . 3 , 2 TST
4 2

=
O CaC
, H
2
C
2
O
4
c pK
1
=1,25 v pK
2
=4,27 (pK
1
+pK
2
=5,52) y c
cn bng:
CaC
2
O
4
Ca
2+
+ C
2
O
4
-2

C
2
O
4
-2
+ H
+
HC
2
O
4
-
K
2

HC
2
O
4
-
+ H
+
H
2
C
2
O
4
K
1

1 =
Ca
tnh
4 2
O C
:

44
[C
2
O
4
] = [C
2
O
4
-2
] + [HC
2
O
4
-
] + [H
2
C
2
O
4
]
= [C
2
O
4
-2
].
) (
4 2
H O C


) (
4 2
H O C
= 1 + [H
+
]/K
2
+ [H
+
]
2
/K
1
K
2

pH = 4 th
46 , 0
52 , 5
8
27 , 4
4
) (
10
10
10
10
10
1
4 2
= + + =

H O C

Thay vo ta c:
5
46 , 0 9
10 . 1 , 8
1 . 1
10 . 10 . 3 , 2
S

= = M/l
V d: Tnh tan S ca Cu
2+
trong nc bit T
CuS
= 6,3.10
-36

H
2
S c pK
1
=7; pK
2
= 12,89 phc Cu
+2
vi OH
-
c:
0 , 7 lg
1
= ; 68 , 13 lg
2
= ; 17 lg
3
= ; 0 , 5 , 18 lg
4
=
V tan ca CuS rt b nn nng ca Cu
+2
v S
-2
khng lm thay
i pH dung dch, nn chp nhn pH dung dch bng pH ca nc l 7 20
o
C.
1
) (
=
OH Cu
+ 10
7
.10
-7
+ 10
13,68
.(10
-7
)
2
+ 10
17
.(10
-7
)
3
+ 10
18,5
.(10
-7
)
4

= 10
0,39

89 , 19 2 7 89 , 12 7
) (
10 / ) 10 ( 10 / 10 1

+ + =
H S


19 , 6 89 , 5 89 , 5
10 10 10 1 = + + =

5 , 0 19 , 6 39 , 0 36
) 10 . 10 . 10 . 36 , 6 (

= s

36 , 14
10

= M/l
Nu khng k n
Cu
v
S
th tan S l 10
-17,6
M/1. Nh vy S ln hn S
trn 1000ln.
5.3.3. nh hng ca s to phc.
S to phc vi cc ion ca kt ta c th xy ra theo 2 trng hp:
- To phc vi cht l.
- To phc vi ion ca kt ta.
Ta xt 2 trng hp ny.
To phc vi cht l.
Vi kt ta M
m
A
n

M
m
A
n
mM + nA

45
Mt ion a t ngoi to phc vi cation kim loi: ML, ML
2
,. ML
p
. Nu A c
phn ng ph th tan ca M
m
A
n
c tnh nh cng thc (5.5). iu quan trng
l cn bit nng cn bng ca cc phi t tnh c .
V d: Tnh tan ca AgCl v AgI trong dung dch amoniac 3,3M. Trong dung
dch c cc cn bng sau:
AgX Ag
+
+ X
-

Ag
+
+ NH
3
Ag(MH
3
),
1

Ag(NH
3
) + NH
3
Ag(NH
3
)
2 2

Vi T
AgCl
= 1,8.10
-10
; T
AgI
= 1.10
-16


lg
1
= 3,3 lg
2
= 7,1

Nng amoniac rt cao, cao hn nhiu nng [Ag
+
] nn ta coi [NH
3
] =
3,3
| | | |
2
3 2 3 1 ) (
1
3
NH NH
NH Ag
+ + =
= 1+ 10
3,3
.3,3+10
7,1
.3.3
2
= 10
8,1

S
AgCl
=

(1,1.10
-10
.10
8,1
)
0,5
= 10
-1
M
S
AgI
= (10
-16
.10
8,1
)
0,5
= 10
-4
M
tan ca AgCl ln gp 1000 ln tan ca AgI trong dung dch ammoniac
3,3M.
To phc vi ion ca kt ta.
Nhiu thuc th kt ta, lc cho d kt ta tan ra. V d:
- Cc hydroxid lng tnh nh Al(OH)
3
,Zn(OH)
3

Al(OH)
3
+ OH
-
Al(OH)
4
-

- Cc halogenid
Hg
+2

+ 2I
-
HgI
2

HgI
2
+ 2I
-
HgI
4
-2

Nh vy khi cho thuc th to kt ta vo dung dch, nng ion c kt
ta s gim dn ri t cc tiu. Nu thm tip thuc th tan ca ion ny li tng
ln.
5.4. Phng php chun kt ta:
5.4.1. Nguyn tc:
L phng php nh lng da trn vic dng phn ng kt ta (to thnh
hp cht t tan) gia thuc th v cht cn nh lng.

46
Phng php kt ta gip ta nh lng cc anion nh Cl
-
, Br
-
, CN
-
, SCN
-
,
SO
4
2-
, CrO
4
2-
,PO
4
3-
v.v v ngc li nh lng cc cation to thnh ta vi cc
anion trn.
V d: Ag
+
+ Cl
-
AgCl.
5.4.1.1. Phn loi:
Ngi ta phn loi phng php kt ta nh sau:
- Phng php bc: da trn vic dng dung dch chun AgNO
3
, da trn kh
nng to thnh mui bc.
- Phng php thu ngn I: Da trn vic dung dung dch chun mui thu ngn
(I), to thnh hp cht thu ngn I khng tan nh Hg
2
Cl
2
, Hg
2
Br
2
, Hg
2
I
2
.
- Phng php thu ngn II: Da trn vic dung dung dch chun mui thu
ngn (II) to thnh hp cht thu ngn II km phn ly: HgCl
2
, Hg(CN)
2
,
Hg(SCN)
2

Tuy nhin cc phng php thu ngn (I), (II) c nhc im l mui thu
ngn rt c nn t s dng.
5.4.1.2. Yu cu i vi phn ng trong phng php kt ta.
Khng phi tt c cc phn ng kt ta u c th dung xc nh nh
lng. Cc yu cu c bn i vi cc phn ng c dng trong phng php kt
ta l:
- Phn ng gia cht cn xc nh (A) v dung dch chun ca thuc th B cn
phi xy ra vi iu kin to thnh kt ta c tan
m m
B A
S ti thiu, v trong
mi trng hp khng c vt qu tan cho php 10
-5
mol/l. Phc to
thnh phi c hng s khng bn nh nht, hng s ny biu th mc bn
ca phc.
- V thm cc cht in ly khng c ion chung i vi kt ta A
m
B
n
lm tng
tan ca n nn phn ng cn tin hnh iu kin khi cht l c mt trong
dung dch phn tch khng cn tr s chun cht cn xc nh, phn ng
kt ta kt thc nhanh v thc t n tn cng.
5.4.2. Phng php bc:
y ta kho st bng hai phng php thng dung:
5.4.2.1. Phng php Mohr:
* Nguyn tc:
Da vo phn ng Cl
-
tc dng dung dch tiu chun AgNO
3
vi ch th mu
K
2
CrO
4
.
Cc phn ng:

47
- Bt u chun n trc im tng ng ch xy ra phn ng.
Ag
+
+ Cl
-
AgCl (mu trng) T
AgCl
= 10
-10

- Sau im tong ng, ion Ag
+
d trong dung dch s tc dng vi ion
CrO
4
2-
.
2Ag
+
+CrO
4
2-
Ag
2
CrO
4
(mu gch)
12
Ag
10 T
4 2

=
CrO
* c im v iu kin ca phng php:
sai s khng qu + 0,1% phng php cn chun trong iu kin:
- im kt thc ph thuc vo nng ca ch th nn cn tnh nng K
2
CrO
4

cn thit cho vo.
V d: ti im tng ng nng cn thit ca Ag
+
kt ta Cl
-
.
[Cl
-
] = [Ag
+
] =
5 10
10 10

= (iong/l)
Vy nng cn thit ca Ag
+
to kt ta ion CrO
4
-
l:
| |
| |
2
2 5
12
2
- 2
4
10
) 10 (
10
CrO
4 2

+
= = =
Ag
T
CrO Ag
(iong/l)
Nh vy nng ca ch th trong khong t 10
-2
n 10
-3
M nu m qu
mu vng ca ion cromat s cn tr vic nhn ra mu gch ca kt ta, kh xc
nh c im tng ng:
Vic s dng ch th cromat l da vo nguyn tc kt ta phn on tc
Ag
+
+Cl
-
AgCl trc sau mi n Ag
+
+ CrO
4
2-
Ag
2
CrO
4
nh vy C
Ag+

trng hp 2 phi ln hn C
Ag+
trng hp 1.
V d:Gi s ta c dung dch cha hai ion Cl
-
v CrO
4
2-
vi nng :

2
CrO Cl
10 C C
- 2
4
-

= = (iong/l)

+
Ag
C to kt ta vi ion Cl
-
l:

8
2
10
Cl
AgCl
Ag
10
10
10
C
T
C
-

= = =
+
(iong/l)

+
Ag
C to kt ta vi ion CrO
4
2-
l:

10
2
12
CrO
CrO Ag
Ag
10
10
10
C
T
C
- 2
4
4 2

= = = +
=10
-5
(iong/l)
Vy nng ion Ag
+
khi tc dng ion Cl
-
nh hn 1 000 ln khi tc dng ion
CrO
4
2-

48
- Mi trng chun nm trong khong pH: 6,5 10,2. chnh xc ca php
phn tch ph thuc vo pH ca dung dch.
- Nu dung dch c pH < 7 dn Ag
2
CrO
4
tan ln khng to c kt ta ca ch
th (v mui baz yu tham gia phn ng thu phn).
- Nu dung dch c pH > 10 (baz) s c phn ng ph:
Ag
+
+ OH
-
AgOH
Ag
2
O + H
2
O
- Khng dng phng php ny xc nh ion I
-
, SCN
-
v cc kt ta AgSCN,
AgI hp th mnh ion CrO
4
2-
nn s chuyn mu ca ch th khng r.
* ng dng: - Ch yu xc nh Cl
-
, Br
-

- Tnh ton kt ta theo chun trc tip.

5.4.3.2. Phng php Folgahr.
* Nguyn tc:
Da vo phn ng Cl
-
tc dng lng d chnh xc ca dung dch tiu chun
AgNO
3
, lung d AgNO
3
c chun bng dung dch tiu chun SCN
-
vi ch
th phn Fe
3+

Cc phn ng xy ra:
- t lc chun n trc im tng ng ch xy ra phn ng:
Ag
+
+ Cl
-
AgCl
(t rng)
(T
AgCl
= 10
-10
)
- Lng Ag
+
d c chun bng CNS
-
vi phn ng chun :
Ag
+
+ SCN
-
AgCNS
(t rng)
(T
AgCNS
=10
-12
)
- Sau khi lng Ag
+
ht, lng CNS d phn tc dng Fe
3+

CNS
-
+Fe
3+
[Fe(CNS)]
2+

(dung dch mu)
Ch : do T
AgCl
= 10
-10
v T
AgCNS
= 10
-12
do tan ca AgCl > AgCNS nn
ti im cui bc nhy s xy ra phn ng
AgCl Ag
+
+ Cl
-
10
-10
Ag
+
+ SCN
-
AgSCN 10
-12
AgCl + SCN
-
AgSCN +Cl
-

Do vy mun xut hin mu mu ca Fe phi cho thm mt lng CNS
-

,
iu ny gy ra sai s cho php chun , trnh hin tng trn n gin l lc
b kt ta AgCl trc ri mi chun lng d.
*c im v iu kin phng php.

49
- Ch th c nng 10
-2
n 10
-3
M.
- Mi trng chun l axt trnh cc hin tng sau:
- S thu phn ca mui Fe
3+
.
- S to Ag
2
O.
- S hp thu kt ta.
5.4.4.ng dng:
Phn ln chun o bc thng thc hin bng chun ngc theo
phng php Volhard. AgNO
3
y c dng nh l cht gc. Dung dch chun
KSCN c chun li vi dung dch AgNO
3.
Bng (5.1) tm tt cc ion c th c
chun bng phng php bc.
Ngoi ra, ngi ta cn dng chun kt ta vi cc thuc th khc nhau
nh Hg
2
(NO
3
)
2
, BaCl
2
, Pb(NO
3
)
2
, K
4
Fe(CN)
6
. Nht l hin nay gi thuc th gc
AgNO
3
cao nn ngi ta c khuynh hng dng Hg
2
(NO
3
) thay th:
Bng 5.1
Cht c chun Ch th Ghi ch
Br
-
, I
-
, AsO
4
-3
, CN
-
, CNO
-
, Volhard Khng cn loi kt ta ca bc
CO
3
-
, CrO
4
-2
, CN
-
, Cl
-
,PO
4
-3
,
S
-2

Volhard Loi kt ta trc lc chun
bc d
K
+
Volhard ci
tin
Kt ta K
+
vi B(C
6
H
5
)
4
-
, d thm
Ag
+
d c AgB(C
6
H
5
)
4
v
chun Ag
+
d bng KCSN
Br
-
, Cl
-

SeO
4
-2
, Br
-
, Cl
-
, I
-

Mohr,
ch th hp ph
Chun trc tip
Zn
+2
Volhard ci
tin
Kt ta ZnHg(SCN)
4
, lc, ho tan
trong acid. Thm Ag
+
d v chun








50
Chng 6
PHN NG TO PHC - PHNG PHP TO PHC

6.1. Phc cht.
6.1.1 nh ngha v danh php
6.1.1.1 nh ngha
Thng thng khng c mt nh ngha tng qut no tho mn ng v
phc cht. y c th nh ngha nh sau:
Phc cht l loi hp cht sinh ra do ion n ( thng l ion kim loi ) gi l
ion Trung tm, ho hp vi phn t hoc ion khc gi l cc phi t. Trong dung
dch ion trung tm, phi t v phc cht u tn ti c lp ring r.
Trong thnh phn ca phc cht bao gm : ion trung tm ( cc ion kim loi )
v cc phi t l cc phn t hay ion to thnh cu ni c vit trong du [ ], cc
ion tri du vi cu ni ca phc l cc cu ngoi c vit ngoi du [ ].
Phc cht c hnh thnh khi phn t ca hai cht kt hp vi nhau.
CuSO
4
+ 4NH
3
[Cu(NH
3
)
4
]SO
4
HgI
4
+ 2KI K
2
[HgI
4
]
Trong dung dch phc cht phn ly thnh ion phc v ion n gin.
[Cu(NH
3
)
4
] SO
4
[Cu(NH
3
)
4
]
2+
+ SO
4
2-

K
2
[HgI
4
] 2K
+
+ [HgI
4
]
2-

Ion phc bao gm :
-Nguyn t trung tm ( ion trung tm ) : Cu
2+
, Hg
2+

-Cc phn t hay ion phi t gi l cc phi t nm xung quanh ion trung tm
theo trt t hnh hc xc nh.
6.1.1.2 Phn loi phc cht
Da vo thnh phn ca phc c th chia chng thnh ba loi:
-Phc Aminoacat : l phc cht trong phi t l cc phn t amoniac.
[Cu(NH
3
)]SO
4
[Co(NH
3
)
6
]Cl
3
[Pt(NH
3
)
6
]Cl
4

-Phc cht aqu : l phc cht trong phi t l cc phn t nc.
[Co(H
2
O)
6
]Cl
2
[Al(H
2
O)
6
]Cl
3
[Cr(H
2
O)
6
]Cl
3

-Phc cht axido : l phc cht trong phi t l cc anion.
K
2
[PtCl
6
] K
4
[Fe(CN)
6
] H
2
[SiF
6
] [Co(NO
2
)
6
]
3-

51
Ngoi ra cn c phc cht anion l cc phn t hu c gi l cc hp cht ni
phc:

6.1.1.3 Cch c tn
Trc khi c tn cn phi xc nh:
- Xc nh cu ni, cu ngoi.
- Xc nh mc oxy ho ca cation cu ni.
+ c tn cu ni trc : c tn anion v thm vn ui o
Cl
-
: cloro CN
-
: xiano SO
3
2-
: sunfito SO
4
2-
: sunfato
OH
-
: hiroxo. . . .
+ c tip tn phi t trung ho vi cc thut ng.
NH
3
- amin H
2
O - aqu
+ Sau c tn cht to phc (cation) dng gc tn platin v thm vn ui at
v mc oxy ho ca cht to phc bng s la m trong ngoc n. Cui cng c
tn cation hay anion cu ngoi.
V d: K[Fe(NH
3
)
2
(CN)
4
] tetraxiano iamin feriat (III) kali
(NH
4
)
2
[Pt(OH)
2
Cl
4
] tetracloro ihiroxo platinat (IV) amoni
Cr(H
2
O)
3
F
3
[Co(NH
3
)
3
(NO)
2
Cl] cloro initrito triamin cobanat (III)
[Pt(NH
3
)
4
Cl
2
]Cl
2

K
4
[Fe(CN)
6
] hecxaxyano ferat (II) kali
Fe
4
[Fe(CN)
6
]
3
hecxaxyano ferat (II) st (III)
Fe
3
[Fe(CN)
6
]
2
hecxaxyano ferat (II) st (II)
[Co(SCN)(C
2
O
4
)(NH
3
)
3
]
6.1.2 bn ca phc cht v ngha
6.1.2.1 bn ca phc

52
Phn ly
t o thnh
Trong dung dch phc cht c cn bng thun nghch: phn ly v to thnh.
Gi s c kt ta M
n
L
m
( n gin b qua vic ghi in tch ca cc ion).
M
n
L
m
nM + mL
Hng s cn bng i vi qu trnh phn li phc c gi l hng s khng
bn K ca phc cht.
K
Cb
=
] [
] [ ] [
m n
m n
L M
L M
(1)
Hng s cn bng i vi qu trnh to phc cht gi l hng s bn ca
phc.
=
m n
m n
L M
L M
] [ ] [
] [
(2)
Qua (1) v (2) ta thy hng s bn l nghch o ca hng s khng bn
ca phc (hng s cn bng K) v ngc li.
=
Cb
K
1
(6.1)
Phc cht cng bn vng ( t phn li ) nu hng s bn ca n cng ln.
V d:
[Cd(NH
3
)
4
]
2+

Cd
2+
+ 4NH
3

=
4
3
2
2
4 3
] ][ [
] ] ) ( [[
NH Cd
NH Cd
+
+
cn K
Cb
=
+
+
2
4 3
4
3
2
] ) ( [
] ][ [
NH Cd
NH Cd
=2,5.10
-7

[Cu(NH
3
)
4
]
2+

Cu
2+
+ 4NH
3

=
4
3
2
2
4 3
] ][ [
] ) ( [
NH Cu
NH Cu
+
+
cn K
Cb
=
+
+
2
4 3
4
3
2
] ) ( [
] ][ [
NH Cu
NH Cu
=4,6.10
-14

Vy phc [Cu(NH
3
)
4
]
2+
bn hn phc [Cd(NH
3
)
4
]
2+

6.2. Phng php nh lng to phc
(Phng php chun bng dung dch Complexon )
6.2.1 S lc v complexon
Phng php nh lng bng complexon l phng php da trn phn ng
to phc ni ca nhiu ion kim loi vi mt s thuc th hu c gi chung l cc
complexon .
Cc complexon l cc axit amin polycarboxylic v cc dn xut ca chng c
Scharzenbach nghin cu k nm 1940-1945.
a. Complexon I : axit nitril triaxetic (NTA) Trilon A, vit tt : H
3
Y

53

b. Complexon II : trilon B; etylen diamin tetra axit axetic, vit tt H
4
Y

y l mt axit hu c c a chc, phn ly 4 nc ty thuc vo pH mi trng
H
4
Y H
3
Y
-
+ H
+
pk
1
= 2,0
H
3
Y
-
H
2
Y
2-
+ H
+
pk
2
= 2,73
H
2
Y
2-
HY
3-
+ H
+
pk
3
= 6,24
HY
3-
Y
4-
+ H
+
pk
4
= 10,34
c. c. complexon III : trilon B, mui inatri ca EDTA, vit tt: Na
2
H
2
Y

Ngoi s khc nhau v phn t lng c im to phc ca 2 dung dch
complexon ny u ging nhau.
d. complexon IV

6.2.2 c im to phc ca EDTA
Trong cc dung dch complexon trn th dung dch complexon III c s
dng nhiu nht, v n l mt cht gc, d tan, to phc bn vi cc ion kim loi,
trong phng trnh phn ng t l lun xy ra v s mol gia EDTA v ion kim
loi l 1:1 v gii phng ton b ion H
+
c trong EDTA.
Na
2
H
2
Y + M
n+
= MY
(4-n)-
+2H
+
+ 2Na
+

V vy
+ n
M
=
2
M

EDTA
=
2
EDTA
M


54
EDTA l axit hu c c 4 ln axit, s to phc MY
(4-n)-
ph thuc vo pH
mi trng, phc cng bn khi pH cng thp, da trn kh nng ny ngi ta chia
cation thnh 3 nhm.
- Nhm phc cht hnh thnh mi trng axit mnh(pH : 1-2). Gm cc cation
ho tr +3, +4 nh Fe
3+
, Cr
3+
. . .
- Nhm phc cht hnh thnh mi trng axit yu (pH : 4-5) gm cc kim loi
nng ho tr 2 nh Zn
2+
, Pb
2+
, Cu
2+
, Co
2+
, Ni
2+
, Fe
2+
. . .
- Nhm phc cht hnh thnh mi trng pH 10. Gm kim loi kim th. Cc
phc ny c hng s bn cng ln phc cng bn bi vy s c s cnh tranh to
phc.
V d : CaY
2-
c K
b
=10
10,7
> hng s bn ca MgY
2-
l 10
8,7
do nu thm
MgY
2-
vo dung dch Ca
2+
th :
Ca
2+
+ MgY
2-
CaY
2-
+ Mg
2+

Hoc nu thm dung dch complexon vo dung dch c cha Ca
2+
, Mg
2+
th
Ca
2+
s to phc trc .



Bng 6.1 Hng s bn ca mt s complexon
ion K
b
Ion K
b
ion K
b
ion K
b

Fe
3+
10
25,1
Zn
2+
10
16,3
Ca
2+
10
10,7
Bi
3+
10
22,8
Th
4+
10
23,2
Cd
2+
10
16,4
Mg
2+
10
8,7
Cu
2+
10
18,8

Hg
2+
10
28,1
Al
3+
10
16,1
Ba
2+
10
7,8
Ni
2+
10
18,6

Pb
2+
10
18
Fe
2+
10
14,3
Ag
+
10
7,3
Co
2+
10
16,3

6.2.3 Cht ch th mu
xc nh im tng ng trong phng php complexon ngi ta dng
ch th mu kim loi, l cc hp cht hu c, c kh nng to phc vi ion kim
loi phc c mu v trong iu kin xc nh, mu ca phc khc vi mu ca
cht ch th t do.
Cc cht ch th thng dng
1. Eriocrom T en : C
20
H
13
O
7
N
3
S (ET-00)

55

pH=10 ch th c mu xanh, khi to phc cc ion Mg
2+
, Zn
2+
, Pb
2+
. . . c
mu nho.
2. Murexit : C
8
H
8
O
6
N
6
. H
2
O ( amoni purpurat )

pH=11 murexxit c mu tm (H
3
Ind
-
) to phc vi Ca
2+
cho phc mu.
6.2.4 Cc k tht chun bng EDTA
6.2.4.1. Chun trc tip. y l phng php n gin nht .
Ly dung dch cn nghin cu v iu chnh pH thch hp bng cc dung
dch m, sau t Buret ( thng dung dch tiu chun complexon III) cho vo
dung dch chun n khi ch th i mu, t ch th to phc n ch th t do.
V d: Chun Mg
2+
bng EDTA vi ch th eriocrom T-en (ET_OO)
pH=10
-Lc u c mu nho, do phi ng Mg
2+

vi cht ch th.
Mg
2+
+ HInd
2-
MgInd
-
+ H
+
-Khi nh EDTA xung, Mg
2+

t do s phn ng trc.
Mg
2+
+ HY
3-
MgY
2-
+ H
+
Lc ny mu ca dung dch vn khng i, gn im tng ng ta c s
cnh tranh to phc.
HY
3-
+ MgInd
-
MgY
2-
+ HInd
2-

xanh

6.2.4.2. Chun thay th.
V d: nh lng Ca
2+
, ta thm MgY
2-
vo dung dch, v phc Ca
2+
vi
EDTA bn vng hn ca Mg
2+
nn
Ca
2+
+ MgY
2-
CaY
2-
+ Mg
2+


56
nh lng Mg
2+
b y ra bng EDTA theo phng php trc tip trn.
T xc nh hm lng Ca
2+
.
6.2.4.3. Chun ngc (d).
Ly ion cn xc nh cho tc dng mt lng d chnh xc EDTA, lng d
ca EDTA c chun bng dung dch tiu chun Mg
2+
(thay Zn
2+
).
Cc phn ng xy ra:
M
n+
+ HY
3-
MY
(4-n)-
+ H
+
d
HY
3-
+ Mg
2-
MgY
2-
+ H
+
Mg
2+
+ HInd
2-
MgInd
-
+ H
+
Xanh nho
6.2.4 ng dng:
6.2.4.1. nh lng Ca
+
.
Bng complexon III trong mi trng kim vi ch th murexid:
Murexid trong mi trng kim c mu tm (H
2
Ind
3-
), kt hp vi Ca
2+
to
thnh phc c mu (CaHInd
-
). Khi thm complexon vo, gn im tng
ng c phn ng cnh tranh to phc:
HY
3-
+ CaHInd
-
= CaY
2-
+ H
2
Ind
3-

() (tm)
6.2.4.2. Xc nh cng ca nc:
cng ton phn ca nc l tng mui calci m magnesi tan trong nc.
C th xc nh cng ton phn bng complexon III vi ch th l en ericrom T.
Ly mu nc cn nh lng, cho thm ch th en ericrom T vo, ch th s
to phc mu vang vi mt phn Mg
2+
trong mu. Khi nh EDTA vo, EDTA s
phn ng vi Ca
2+
t do, sau vi Mg
2+
t do (v phc CaY
2-
bn hn phc
MgY
2-
), n ln cn im tng ng EDTA s ph phc ca ch th vi Mg
2+
gii
phng ra ch th c mu xanh.
Ghi ch: cng ton phn thng c tnh nh sau:
- cng c: ng vi 1 gam CaO trong 1000 lt nc (nc 4
0
: rt mm;
nc 4 8
0
: mm; nc 8 16
0
: nc va; nc 16 24
0
: nc cng)
- cng Php: ng vi 1 gam CaCO
3
trong 100lit.
6.2.4.3. nh lng Fe
3+
.
Trong mi trng acid (ph 2- 3) EDTA tc dng vi Fe
3+
mt phc cht m
vng nht FeY
-
. Nu dng ch th l acid salicylic hay acid sulfosalicylic pH n

57
tc dng vi Fe
3+
to thnh phc c mu hng. Ti im tng ng mu hng
bin mt v dung dch c mu vng nht.
6.2.4.4. nh lng Ba
2+
(theo phng php chun ngc).
Cho Ba
2+
cn nh lng, tc dng vi mt lng d chnh xc EDTA. nh
lng EDTA d bng dung dch Mg
2+
.
6.2.4.5. nh lng SO
4
2-
(phng php gin tip).
Cho BaCl
2
d kt ta hon ton SO
4
2-

Ba
2+
+ SO
4
2-
= BaSO
4

nh lng Ba
2+
cn li bng complexon III. quan st d dng s chuyn
mu ca ch th, thm vo dung dch lng Mg
2+
nht nh v qu trnh nh lng
tin hnh hon ton tng t nh nh lng cng ton phn ca nc.






















58
Chng 7
PHN NG OXY HO - KH
PHNG PHP CHUN OXY HO - KH

7.1. Th oxy ho - kh.
7.1.1. nh ngha phn ng oxy ho - kh:
nh ngha:
Phn ng oxy ho - kh l phn ng cho nhn in t gia cht kh l cht
oxy ho
a kh
1
+ b ox
2
b ox
1
+ b kh
2.

v d: Khi nhng mt thanh kim loi km vo dung dch ngsunfat s xy
ra phn ng:
Zn
0
+ Cu
2+
Cu
0
+ Zn
2+


Zn - 2e = Zn
2+

Cu
2+
+ 2e = Cu
0

S khc nhau gia phn ng axit - baz v phn ng oxy ho - kh
Trong phn ng axit - baz qu trnh cho nhn proton, to ra cp axit - baz lin
hp: Baz + H
+
Axit. Tng t dng oxy ho nhn in t bin thnh dng kh
to ra cp oxy ho - kh lin hp. Tuy nhin 2 phn ng ny c nhng im khc
nhau.
- Phn ng oxy ho - kh tc l qu trnh cho nhn in t c th thc hin
trong cc dung dch ring r. Cn qu trnh chuyn proton t axit sang baz
c thc hin trc tip trong mt dung dch.
- Tc phn ng axit - baz thng xy ra nhanh, tc thi. Phn ng oxy
ho - kh thng chm, v nhiu giai on do vy thng phi tng nhit
, thm cht xc tc. . .
- Phn ng axit - baz thng c s tham gia ca dung mi nc, bn thn
nc ni ring l phn t dung mi ni chung l sn phm ca phn ng
axit - baz, c th cho hoc nhn proton.
2H
2
O + 2e 2OH
-
+ H
2

2H
2
O O
2
+ 4H
+
+ 4e
Trong qu trnh oxy ho - kh ngi ta tm cch trnh qu trnh oxy ho
hoc kh ca nc.

59
7.1.2. Th oxy ho - kh v cc yu t nh hng:
7.1.2.1. Th oxy ho - kh
Trong mt cp oxy ho - kh. Dng oxy ho cng d nhn in t th tnh oxy
ho ca n cng mnh v dng kh lin hp vi n cng yu. c trng cho
kh nng cho nhn in t ca mt cp oxy ho - kh ngi ta dng i lng
th oxy ho - kh v c tnh theo phng trnh Nerst:

| |
| | kh
ox
n
E E lg
059 , 0
0
+ = (7.1)
Ch :
- Trong nhiu trng hp khi dung dch long thng thay hot bng nng
cn bng trong phng trnh Nerst.
- Trong phn ng nu dng oxy ho, dng kh l cc cht rn khng ho tan hay
cht kh. . . th nng ca n coi nh bng n v.
V d 1:
Zn
2+
+ 2e Zn
0

| |
+
+ =
+
2 0
lg
2
059 , 0
0
2
Zn E E
Zn
Zn

- Trong bn phn ng phc tp c nhiu cu t tham gia, u a vo phng
trnh Nerst.
a ox + m H
+
+ n e a kh + p H
2
O

| | | |
| |
'
lg
059 , 0
a
m
a
kh
ox
kh
H ox
n
E E
+
+ = (7.2)
Nc l dung mi, coi nh l hng s khng a vo phng trnh.
V d 1: Tnh th in cc Platin khi nhng in cc ny vo dung dch KBr
0,01M bo ho Brom
Br
2
bh + 2e 2Br- v E
Br
Br
065 , 1
0
2
2
=

| |
( )
v
Br
E 183 , 1
01 , 0
1
lg
2
059 , 0
065 , 1
1
lg
2
059 , 0
065 , 1
2 2
= + = + =


V d 2: Mt si dy bc c nhng vo trong dung dch AgNO
3
. Th in
cc o c l: 0,6825. Tnh nng Ag trong dung dch bit:
Ag
+
+ 1e Ag0 v E
Ag
Ag
800 , 0
0
=
+
+


60
| |
+
+ =
+
+
Ag E E
Ag
Ag
lg
1
059 , 0
0

Thay s:

| |
| | M Ag
Ag
2
10 . 000 , 1
lg 059 , 0 800 , 0 680 , 0
+
+
=
+ =

7.1.2.2. Cc yu t nh hng n th oxy ho - kh:
a. nh hng ca pH mi trng:
a ox + n e + m H+ a kh + x H
2
O

| | | |
| |
'
0
lg
059 , 0
a
m
a
kh
ox
kh
ox
kh
H ox
n
E E
+
+ =
Do vy | |
+
H nh hng rt ln n th oxy ho - kh ca phn ng, v c
th lm thay i chiu ca phn ng
v d:
AsO
4
3-
+ 2I
-
+ 2H
+
AsO
3
3-
+ I
2
+ H
2
O (1)
Cho: | | | | l iong AsO AsO / 1 , 0
3
3
3
4
= =


Bn phn ng:
AsO
4
3-
+ 2e + 2H
+
AsO
3
3-
+ H
2
O v E
AsO
AsO
57 , 0
0
3
3
3
4
=

2I
-
- 2e = I
2
v E
I
I
54 , 0
0
2
2
=

0 = pH

| | | |
| |
v E
AsO
H AsO
E E
57 , 0
1 , 0
1 , 0
lg
2
059 , 0
57 , 0
lg
2
059 , 0
3
3
2
3
4 0
= + =
+ =

+

8 = pH
| | | |
| |
( )
v E
AsO
AsO
E E
1 , 0
2
64 . 059 , 0
57 , 0
1 , 0
10 . 1 , 0
lg
2
059 , 0
57 , 0
10
lg
2
059 , 0
64
3
3
2
8
3
4 0
=

+ = + = + =

Nh vy 8 = pH th I
2
s oxy ho c AsO
3
3-
thnh AsO
4
3-
phn ng xy
ra theo chiu nghch li.
b. nh hng ca nng cc cht tham gia phn ng:

61
nh hng do s to kt ta:
Khi dung dch cha ion to c vi dng oxy ho hay dng kh nhng cht
kh tan, in th dung dch cng b thay i mt cch ng k.
V d: Xc nh Cu
2+
bng phng php Iod-Thiosunfat
2Cu
2+
+ 4I
-
2CuI + I
2


v E
v E
Cu
Cu
I
I
17 , 0
54 , 0
0
0
2
2
2
=
=
+
+

Nu tnh theo in th chun th phn ng s xy theo chiu ngc li nhng
do sn phm to kt ta CuI lm gim mnh nng Cu
+
do lm thay i th
oxy ho - kh ca cp
+
+
Cu
Cu
2
.
V d: Gi s: | | l iong I / 10
1
= vi
12
10

=
CuI
T

| |
| |
| |
| |
| |
+
+

+
+ =
+ + = + =
= = =
+
+
+
+
2
2
11
2
11
1
12 12
2
lg 059 , 0 819 , 0
lg 059 , 0 11 . 059 , 0 17 , 0
10
lg 059 , 0 17 , 0
/ 10
10
10 10
2
2
Cu E
Cu
Cu
E
l iong
I
Cu
Cu
Cu
Cu
Cu


Nh vy
+
+
Cu
Cu
E
2
vn ln hn th cp

I
I
E
2
2
nn phn ng xy ra theo chiu
thun
nh hng do s to phc:
Nu trong dung dch c cht to phc vi dng oxy ho hay dng kh th nng
cc cht tham gia phn ng cng thay i dn n th oxy ho - kh cng thay
i theo.
v d: Khi thm KCN vo dung dch [Fe(CN)
6
]
3-
v [Fe(CN)
6
]
2-
c to thnh,
nhng do phc feri km bn lun do th ca dung dch cng gim.

| | | |
( ) | | ( ) | | l iong CN Fe CN Fe
v E
l iong Fe Fe
Fe
Fe
/ 1
77 , 0
/
2
6
3
6
0
2 3
2
3
= =
=
= =

+ +
+
+

Th v E 356 , 0 =
7.1.3. Hng s cn bng v xt mc hon ton ca phn ng oxy ho - kh:

62
7.1.3.1. Hng s cn bng:
Gi s ta c phn ng oxy ho - kh:
a kh
1
+ b ox
2
a ox
1
+ b kh
2

Theo nh lut tc dng khi lng ta c:

| | | |
| | | |
b a
b a
ox kh
kh ox
K
2
'
2
'
2 1
=
C cc bn phn ng:
a ox
1
+ ne = a kh
1

0
1
2
kh
ox
E
b ox
2
+ ne = b kh
2

0
2
1
kh
ox
E

Khi phn ng t n trng thi cn bng ta c:

| |
| |
| |
| |
'
2
2 0
'
1
1 0
lg
059 , 0
lg
059 , 0
2
2
2
2
1
1
1
1
b
b
kh
ox
kh
ox
a
a
kh
ox
kh
ox
kh
ox
n
E E
kh
ox
n
E E
+ =
+ =

Do
2
2
1
1
kh
ox
kh
ox T
E E E = =
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
K
kh
ox
kh
ox
n
E E
kh
ox
n kh
ox
n
E E
kh
ox
n
E
kh
ox
n
E
b
b
a
a
kh
ox
kh
ox
b
b
a
a
kh
ox
kh
ox
b
b
kh
ox a
a
kh
ox
=
|
|
.
|

\
|
=
=
+ = +
'
2
2
'
1
1 0 0
'
2
2
'
1
1 0 0
'
2
2 0
'
1
1 0
lg
059 , 0
lg
059 , 0
lg
059 , 0
lg
059 , 0
lg
059 , 0
1
1
2
2
1
1
2
2
2
2
1
1


059 , 0
0
1
1
0
2
2
10
|
|
.
|

\
|

=
kh
ox
kh
ox
E E n
K (7.3)
n: s in t trao i chung gia cht oxy ho v cht kh trong phn ng

0
2
2
kh
ox
E : in th chun ca cp cht oxy ho.

0
1
1
kh
ox
E : in th chun ca cp cht kh.

7.1.3.2. Xt mc hon ton ca phn ng:

63
vi
6
10 > K phn ng xy ra hon ton.
Nh vy: 0
0
> AE Phn ng s xy ra hon ton.
V d: xt mc hon ton ca phn ng:
Sn
2+
+ 2Fe
3+
Sn
+4
+ 2Fe
2+

62 , 0 15 , 0 77 , 0
15 , 0
77 , 0
0
0
0
2
4
2
3
= = A
=
=
+
+
+
+
E
v E
v E
Sn
Sn
Fe
Fe

21 059 , 0
62 , 0
. 2
10 10 = = K Phn ng xy ra hon ton.
7.2. Phng php chun oxy ho - kh.
7.2.1. Yu cu ca phn ng oxy ho - kh trong phn tch th tch:
1. Phn ng phi c mt chiu nht nh.
2. Phn ng phi xy ra hon ton.
3. Phn ng phi nhanh.
phn ng xy ra hon ton ta xt trn, phn ng oxy ho - kh
thng xy ra chm v qua nhiu trung gian tng tc phn ng ngi ta
thng dng mt s bin php sau:
Tng nhit : Khi nhit tng tc phn ng tng khong 2-3 ln
v d: phn ng MnO
4
-
+ C
2
O
4
2-
+ H
+
Mn
2+
+ 2CO
2
+ H
2
O phn ng xy ra
chm, un nng phn ng xy ra nhanh hn.
Tng nng : Trong trng hp khng th tng tc phn ng
bng nhit thng tng nng ca thuc th tng tc phn
ng.
Dng cht xc tc: cc phn ng oxy ho - kh thng xy ra nhiu
giai on trung gian. Cho thm cht xc tc tng tc phn ng.
v d: ion I
-
lm xc tc cho phn ng: oxy ho S
2
O
3
2-
bng H
2
O
2
hay ion
Mn
2+
lm xc tc cho php chun KMnO
4

7.2.2. ng cong chun oxy ho - kh:
Gi s ta c phn ng oxy ho - kh sau:
a kh
1
+ b ox
2
a ox
1
+ b kh
2

C hai bn phn ng:
a ox
1
+ ne = a kh
1

0
1
1
kh
ox
E

64
b ox
2
+ ne = b kh
2

0
2
2
kh
ox
E
C 2 trng hp xy ra
m n =
'
'
a a
a a
=
=

'
'
b b
b b
=
=

m n =
'
'
a a
a a
=
=

'
'
b b
b b
=
=

ng cong chun oxy ho - kh: l ng biu din s bin thin th
in cc ca dung dch khi cho thm dung dch tiu chun vo bnh.
y ta s kho st s bin thin ca th oxy ho - kh trong 2 trng hp
trn:
1. Trng hp m n =
V d: Xy dng ng cong chun khi chun cht kh
1
c th tch V
kh1
,
nng N
kh1
; bng cht oxy ho 2, c th tch V
ox2
, nng N
ox2
.
Phn ng chun :
kh
1
+ ox
2
ox
1
+ kh
2

Bn phn ng:
ox
1
+ ne = kh
1

0
1
1
kh
ox
E
ox
2
+ ne = kh
2

0
2
2
kh
ox
E
phn ng trn xy ra hon ton
0 0
2
2
1
1
kh
ox
kh
ox
E E > hay 0
0
> AE
Th dung dch khi cha chun : trong dung dch ch c cht kh 1 nn
in th do cp
1
1
kh
ox
quyt nh:

| |
| |
1
1 0
lg
059 , 0
1
1
1
1
kh
ox
n
E E
kh
ox
kh
ox
+ =
Do cha chun nn: | | 0
1
= ox v vy
dd
E s tin n v cng =
1
1
kh
ox
E
Nhng trong thc t cc ho cht khng bao gi sch, nn dung dch lun c
mt lng nh cht oxy ho lin hp v khi in th khng bao gi bng 0, nn
in th dung dch c tnh:
0
1
1
1
1
kh
ox
kh
ox
E E = (7.4)

65
Ln cn trc im tng ng (cho thiu 0,1% cht ox
2
vo dung dch)
lc ny trong dung dch tn ti ng thi c 2 cp cht oxy ho - kh, song
do d cht kh
1
nn coi nh nng oxy ho 2 rt nh, v vy in th n
gin c tnh theo cp
1
1
kh
ox

| |
| |
| |
| |
( )
( )
n
N V N V
n
N V
kh
ox
kh
ox
n
E E
ox ox kh kh
ox ox
kh
ox
kh
ox
2 2 1 1
2 2
1
1
1
1
. .
.
lg
059 , 0
1
1
1
1 0

=
+ =

( )
( )
2 2 1 1
2 2
1
1
1
1
. .
.
lg
059 , 0
0
ox ox kh kh
ox ox
kh
ox
kh
ox
N V N V
N V
n
E E

+ = (7.5)
Ti im tng ng: trong dung dch tn ti c hai cp cht oxy ho, kh:
(1)
| |
| |
1
1 0
lg
059 , 0
1
1
1
1
kh
ox
n
E E
kh
ox
kh
ox
+ =

(2)
| |
| |
2
2 0
lg
059 , 0
2
2
2
2
kh
ox
n
E E
kh
ox
kh
ox
+ =
Ti im tng ng do phn ng t trng thi cn bng nn c:
| | | |
| | | |
2 1
2 1
2
2
1
1
kh ox
ox kh
E E E
kh
ox
kh
ox T
=
=
= =

Nhn (1) vi n v (2) vi n v cng (1) v (2) ta c
| | | |
| | | |

1
2 1
2 1 0 0
lg 059 , 0 2
2
2
1
1
kh kh
ox ox
nE nE nE
kh
ox
kh
ox T
+ + =
2
0 0
2
2
1
1
kh
ox
kh
ox
T
E E
E
+
= (7.6)
Ln cn sau im tng ng: trong dung dch cht oxy ho 2 nn c th
coi nng cht kh 1 rt nh, khng ng k, n gin in th c tnh
theo
2
2
kh
ox


66
| |
| |
1 1
1 1 2 2
2
2
2
2
2
2
2
2
.
. .
lg
059 , 0
lg
059 , 0
0
2
2 0
kh kh
kh kh ox ox
kh
ox
kh
ox
kh
ox
kh
ox
N V
N V N V
n
E E
kh
ox
n
E E

+ =
+ =

Nhn xt:
- ng cong chun cng c bc nhy, do in th dung dch thay
i t ngt, thun tin cho vic chn cht ch th mu.
- Dng ng cong i xng (im tng ng nm gia bc nhy
chun )
- Tri s bc nhy chun ph thuc vo cc cp in th chun.
- Bc nhy chun ph thuc:
+ Sai s php chun , sai s ln bc nhy chun di
+ Nng cc cht tham gia phn ng.
2. Trng hp m n = ' a a = ' b b =
V d: Xy dng ng cong chun khi chun cht kh 1 c V
kh1
, N
kh1

bng dung dch cht oxy ho 2 c V
ox2
, N
ox2
.
Phn ng chun :
kh
1
+ ox
2
ox
1
+ kh
2

Bn phn ng:
ox
1
+ ne = kh
1

ox
2
+ me = kh
2

Khi cha chun : in th do cp
1
1
kh
ox
quyt nh:
0
1
1
1
1
kh
ox
kh
ox
E E =
Ln cn trc im tng ng: cho thiu 0,1% ox
2
vo dung dch, lng
d cht khi vn quyt nh in th ca dung dch:
2 2 1 1
2 2
1
1
1
1
. .
.
lg
059 , 0
0
ox ox kh kh
ox ox
kh
ox
kh
ox
N V N V
N V
n
E E

+ = (7.7)
Ti im tng ng: tn ti c 2 cp in th:
| |
| |
| |
| |
) 2 ( lg
059 , 0
) 1 ( lg
059 , 0
2
2 0
1
1 0
2
2
2
2
1
1
1
1
kh
ox
n
E E
kh
ox
n
E E
kh
ox
kh
ox
kh
ox
kh
ox
+ =
+ =


67
Do phn ng t n im tng ng nn ta c:
| | | |
| | | |
2 1
2 1
2
2
1
1
kh ox
ox kh
E E E
kh
ox
kh
ox T
=
=
= =

Nhn (1) vi n v (2) vi m, cng (1) v (2):
( )
| | | |
| | | |

0
2 1
2 1 0 0
lg
2
2
1
1
kh kh
ox ox
mE nE E m n
kh
ox
kh
ox T
+ + = +
m n
mE nE
E
kh
ox
kh
ox
T
+
+
=
0 0
2
2
1
1
(7.8)
Ln cn im tng ng: d 0,1% cht ox
2
vo dung dch, E dung dch do
cp
2
2
kh
ox
quyt nh:
1 1
1 1 2 2
2
2
2
2
.
. .
lg
059 , 0
0
kh kh
kh kh ox ox
kh
ox
kh
ox
N V
N V N V
m
E E

+ = (7.9)
ng cong chun Fe
2+
bng MnO
4
-
c dng:

Nhn xt:
- in th thay i t ngt to nn bc nhy chun .
- Dng ng cong bt i xng: im tng ng nm lch v mt
pha.
- Bc nhy chun ph thuc:

68
+ Sai s
+ Nng
+ Cc cp in th chun.
3. Trng hp m n = ' a a = ' b b =
7.2.3. Cht ch th mu trong phng php oxy ho - kh:
1. Ch th t ch th: phng php pemanganat dung dch tiu chun va l cht
ch th mu, d mt git dung dch KMnO
4
dung dch c mu tm hng.
2. Ch th khng lin quan n in th: Ch th h tinh bt trong phng php
Iod - Thiosunfat. Tc dng I
2
to mu xanh tm.
3. Ch th lin quan n in th: y l cc cht oxy ho - kh hu c yu, c
mu dng phn t khc mu dng ion.
Indox + ne Indkh
0
Indkh
Indox
E

| |
| | Indkh
Indox
n
E E
Indkh
Indox
Indkh
Indox
lg
059 , 0
0
+ =
Nu | | | | Indkh Indox
2
1
> thy c mu dng oxy ho v ngc li.
Khong i mu ca ch th l
n
E E
Indkh
Indox
Indkh
Indox
059 , 0
0
=
a. Ch th iphenylamin:
Dng kh khng mu, dng oxy ho c mu tm m, khi c mt cc cht oxy ho
mnh xy ra cc phn ng sau:

7.2.4. Cc php chun thng dng:
7.2.4.1. Php chun Pemanganat (phng php Pemanganat)
a. Nguyn tc : l php chun da vo kh nng oxy ho mnh ca
KMnO
4
trong mi trng axit :
MnO
4
-
+ 5e + 8H
+
= Mn
2+
+ 4H
2
O

69

5 , 31
5
51 , 1
4
2
4
0
= =
=
+

KMnO
Mn
MnO
M

v E

b. c im v iu kin :
Lun duy tr nng axit cao, dng H
2
SO
4
lm mi trng cho php chun
khng dng HCl lm mi trng.
2KMnO
4
+ 16HCl = 2KCl + 2MnCl
2
+ 5Cl
2
+ 8H
2
O
Trong trng hp khng th trnh ion Cl
-
, phi dng cht bo v MnSO
4
,
Na
2
SO
4
hn ch s nh hng ca ion Cl
-
.
y l php chun t ch th, d mt git KMnO
4
dung dch c mu tm
hng.
Thng gn n im tng ng tc mt mu nhanh v xut hin ion
Mn
2+
lm xc tc cho phn ng.
Dung dch KMnO
4
khng phi l cht gc, d b oxy ho lm lng tp cht
thng ln, v vy phi kim tra nng thng xuyn bng dung dch tiu
chun t cht gc H
2
C
2
O
4
.2H
2
O vi phn ng chun
2MnO
4
-
+ C
2
O
4
2-
+16 H
+
2Mn
2+
+ 2CO
2
+ 8 H
2
O
v E
CO
O C
46 , 0
0
2
2
2
4 2
=

0
E A ca phn ng rt ln phn ng xy ra rt hon ton
c. ng dng:
Chun trc tip : xc nh cc cht tham gia phn ng trc tip vi MnO
4
-

nh : Sn
2+
, Fe
2+
, Sb
3+
, Ti
2+
, NO
2
-
, H
2
O
2
, H
2
C
2
O
4

Chun gin tip : S
2-
, S
2
O
3
2-
, I
-

Chun th: cc cation c kh nng to kt ta vi C
2
O
4
2-
: Ca
2+
, Sr
2+
,
Mg
2+
, Ni
2+
, Co
2+
, Mn
2+
, Cd
2+
, Cu
2+
. . .
7.2.4.2. Php chun Bicromat (phng php Bicromat)
a. Nguyn tc: l phng php nh lng da vo kh nng oxy ho
K
2
Cr
2
O
7
trong mi trng axit.
Cr
2
O
7
2-
+ 6e + 14H
+
= 2Cr
3+
+ 7H
2
O
6
36 , 1
7 2 2
7 2 2
3
2
7 2
0
2
O Cr K
O Cr K
Cr
O Cr
M

v E
=
=
+

70
b. c im v iu kin:
Do th oxy ho - kh ca cp phn ng ny nh hn, v vy c th chun
trong mi trng HCl
K
2
Cr
2
O
7
va l dung dch tiu chun va l cht gc
Do sn phm phn ng to Cr
3+
c mu xanh lc, nn mu vng cam
K
2
Cr
2
O
7
s nh hng v khng thy c s i mu, do vy phi dng
cht ch th mu iphenylamin c Indox + 2e Indkh
76 , 0
0
=
Indkh
Indox
E
Khi xc nh Fe
2+
bng phng php ny cn cho thm H
3
PO
4
vo dung dch,
mc ch ko di bc nhy chun .
c. ng dng
Xc nh Fe
2+
, xc nh tng s lng mn trong t, xc nh S
2
O
3
2-

7.2.4.3. Php chun Iod - Thiosunfat:
a. Nguyn tc: Da qu trnh oxy ho thun nghch.
I
2
+ 2e 2I
-


2
54 , 0
0
2
2
M

v E
I
I
=
=

b. ng dng:
Xc nh cc cht kh mnh: H
2
S, H
2
SO
3
, Sn
2+
, Fe
2+
, Na
2
S
2
O
3
. . .
2Na
2
S
2
O
3
+ I
2
= 2NaI + Na
2
S
4
O
6

Ch th h tinh bt
Trong qu trnh chun , lm mt mu ch th, d 1 git I
2
dung dch c mu
vng.
Xc nh cc cht oxy ho: KMnO
4
, K
2
Cr
2
O
7
, H
2
O
2
, Fe
3+
, Cu
2+
, Cl
2
. . .
Qu trnh ny khng xc nh c trc tip, phi chun thay th lng I
2

c hnh thnh sau phn ng c chun bng Na
2
S
2
O
3.

H
2
O
2
+ 2I
-
+ 2H
+
= I
2
+ 2H
2
O
K
2
Cr
2
O
7
+ KI + HCl I
2
+ 2CrCl
3
+ KCl + H
2
O
I
2
+ 2Na
2
S
2
O
3
= 2NaI + Na
2
S
4
O
6

Nguyn tc khi chun cc cht oxy ho phi dng d KI kh hon ton
cc cht oxy ho ri mi chun .
c. c im v iu kin:

71
Khng c chun trong mi trng pH>9 v xy ra phn ng:
I
2
+ 2OH
-
= IO
-
+ I
-
+ H
2
O
IO
-
l cht oxy ho mnh c th oxy ho S
2
O
3
2-
v SO
4
2-

So I
2
d b thng hoa khi c nhit , khi c nhit ch th h tinh bt cng
km nhy, do vy khng c chun khi dung dch cn nng.
Phc cht gia I
2
v h tinh bt ch thun nghch khi nng I
2
thp nn khi
chun gin tip phi chun n khi dung dch c mu vng rm hoc
mu xanh lc mi cho ch th h tinh bt vo.
Lng KI cho vo dung dch khi xc nh cc cht oxy ho phi d I
2
gii
phng d to phc trong dung dch
I
2
+ KI [KI
3
]
Do khi tin hnh chun mt lc sau mu xanh tm li xut hin tr li.
Dung dch Na
2
S
2
O
3
khng bn trong mi trng axit:
Na
2
S
2
O
3
+ 2H
+
= 2Na
+
+ S + SO
2
+ H
2
O
V vy phi b tr Na
2
S
2
O
3
trn buret
Do I
2
, Na
2
S
2
O
3
khng phi l cht gc nn phi kim tra thng xuyn nng
ca chng
7.3. ng dng ca chun oxyho - kh.
Bng 7.1: Mt s cht oxyho thng dng.
Tn E
0
(V) Cht gc
KMnO
4
1,51 Na
2
C
2
O
4,
As
2
O
3
KBrO
3
1,44 KBrO
3

Ce
+4
1,44 Na
2
C
2
O
4
, As
2
O
3

K
2
Cr
2
O
7
1,33 K
2
Cr
2
O
7

KIO
3
1,24 KIO
3

I
2
0,54 As
2
O
3

Bng 7.1: Mt s cht kh thng dng.
Cht kh E
0
(V) Cht gc
Mui Mo - 0,77 K
2
Cr
2
O
7

72
As
3+

-0,56 As
2
O
3

Na
2
S
2
O
3
-0,08 KIO
3
, I
2

Titan (III) -0,10 K
2
Cr
2
O
7

Nhiu cht oxy ho thch hp thch hp cho vic pha ch dung dch chun (Bng
7.1). Cc cht kh c dng hn ch hn v dung dch ca chng d b oxy ho
bi oxy ca khng kh (Bng 7.2)

























73

Chng 8
PHN TCH CNG C

8.1. i cng v phng php:
Phn tch cng c l khi nim ch nhm cc phng php vt l, phng
php ho l phn tch cc cht, trong phng php ny thng thng s dng
dng c, my mc phc tp o cc i lng vt l, ho l ca cc vt th cn
phn tch.
So vi phng php phn tch ho hc, phng php phn tch cng c trong
nhiu trng hp cho php ng thi xc nh tnh v nh lng vt th cn phn
tch. Ngoi ra bng phng php phn tch cng c cn cho php xc nh hm
lng rt nh ca i tng cn phn tch hoc c th phn tch hng lot mu phn
tch.
V d nng <10
-5
M nh 10
-9
hay 10
-10
M. Phng php ny vn phn
tch c trong khi phn tch ho hc ch c phn tch mu c nng >10
-5
.
Do vy hin nay phng php phn tch cng c c s dng rng ri trong cc
phng th nghim, nht l phng php vi lng mt lnh vc m phng php
phn tch ho hc khng th gii quyt c. Da vo vic o, cc phng php
phn tch cng c c chia thnh 4 nhm:
- Phng php trc quang.
- Phng php in ho.
- Phng php sc k.
- Nhm cc phng php khc
Do thi lng ca chng trnh sau y ch gii thiu 2 phng php chnh
m cc ngnh k thut Nng Lm Ng cn s dng: Phng php trc quang v
phng php sc k.
8.2. Phng php trc quang.
8.2.1. Nguyn tc phng php:
Phng php trc quang l phng php da trn s chuyn thnh phn cht
cn xc nh thnh hp cht hp th nh sang, ri o hp th nh sng suy ra
hm lng hay thnh phn cht cn nghin cu.
nh sng l nhng bc x in t c bc sng ( ) khc nhau v c chia
thnh cc vng:
- Bc sng < 200 n.m . Vng t ngoi chn khng.
- Bc sng t 200 400 n.m . Vng t ngoi.

74
- Bc sng t 400 800 n.m . Vng nhn thy.
- Bc sng > 800 n.m . Vng hng ngoi.
Bc sng nh sng vi : 200 800 n.m c nng lng kch thch
cc in t lin kt sang orbital phi lin kt, nn s hp th nh sng ny dc gi
l quang ph hp th in t.
Trong phng php trc quang thng dng gii t 200 800 n.m (nh sng
nhn thy) nn php o ca bc sng ny cn c gi l phng php so mu.
8.2.2. nh lut Bouger Lambert Beer.
8.2.2.1. nh lut Bouger Lambert Beer l nh lut c bn ca phn tch so
mu, nh lut c xy dng:
Gi s c mt mi trng ng nht cha cht mu c kh nng hp th nh
sng . Cho mt chm nh sng n sc c bc sng v cng Io i qua mi
trng sau khi b cht mu hp th dng sng yu i v ch cn cng I
l
(I
p

coi nh khng ng k) quan h gia I
l
v Io c xc nh theo 2 nh lut:
nh lut 1: (nh lut Bouger Lambert)

l k
o
l
I
I
.
10

= (8.1)
k: h s tt, h s hp th, h s ny ph thuc vo bn cht ca cht hp th
, nng cht hp th v bc sng ca nh sng hp th.
l: chiu di dy hp th (cm) hay chiu di on ng nh sng truyn qua.
nh lut 2 (nh lut Beer):
C k .

E = (8.2)

E : H s tt phn t, h s ny ch ph thuc vo bn cht ca cht mu v

bc sng nh sng hp th . Theo thc nghim gi tr ny khng ln hn 2.10
5
.
C : Nng dung dch cht mu (mol/l. iong/l).
Kt hp 2 nh lut ta c:

l C
o
l
I
I
. . .
10

E
=
t:
l
o
I
I
D lg = D: c gi l mt quang ca dung dch cht mu.
Ta c: l C D . .

E = (8.3)
Qua biu thc ca nh lut ta c th p dng d dng vo vic xc nh
nng cc cht tan bng cch o mt quang ca dung dch cht mu.
8.2.2.2. Phm vi p dng ca nh lut.

75
- nh sng i qua phi l nh sng n sc, bi v nh sng c di sng
khc nhau mt quang dung dch s khc nhau t khng xc nh c
nng dung dch phn tch da vo mt quang ca dung dch tiu
chun.
l C D . .

E = ' '. . ' ' l C D

E =
' C C =
- Vi nhng hp cht mu,nh lut ch p dng mt khong nng xc
nh, ngoi khong mt quang khng t l cng nng , hay dung
dch khng tun theo nh lut.
- nh lut khng p dng cho cc dung dch huyn ph v hunh quang v
cc ng lut c khuych tn nh sng rt ln v nh sng sau khi i
qua dung dch li c bc sng ln hn, lm vic o mt ca quang ph
khng chnh xc.
- nh lut cn b sai lch do nh hng ca qu trnh pha long, i vi
phc km bn s pha long c nh hng ln nht, v vy cn chn nhng
phc cht c bn cao
8.2.2.3. Nhng yu cu i vi hp cht mu.
Trong phng php phn tch so mu cc hp cht mu phi tho mn cc yu
cu sau:
- Phc phi c bn ln v h s hp th phn t ln.
Phc cht cng bn th nh hng ca qu trnh pha long v ca cc phn
ng ph cng gim nn php o t chnh xc cao hn.
H s hp th phn t ph thuc vo bn cht ca cht mu trong dung dch,
nu hp cht c

E ln th nhy ca phn ng cng tng.

V d: Phc: [Cu(NH
3
)
4
]
2+

E =500
Cu - ithizon

E =5000
nhy phc Cu-ithizon > 100 ln [Cu(NH
3
)
4
]
2+

* Phc cht phi c thnh phn xc nh, tc trong dung dch ch c mt phc
mu hnh thnh. Bi v mt phc mu c mt gi tr xc nh

E , nh lut s b vi
phm khi dng dung dch c nhiu cht mu, mun dung dch ch c mt cht mu
cn chn cc iu kin to cht mu nh sau:
- Thuc th phi c tnh chn lc cao, tc ch to mu vi mt ion xc
nh.
V d: Xc nh ion Fe
3+
trong hn hp Al
3+
, Mg
2+
, Ca
2+
th chn thuc th KSCN
ch c Fe
3+
phn ng.

76
- Thuc th phi c nng xc nh, m bo ch c mt phc mu
c hnh thnh, v phn ng to phc thng xy ra nhiu bc:
V d: Phn ng Fe
3+
vi SCN
-
xy ra:
Fe
3+
+ 2SCN
-
= Fe(SCN)
2
+
khi C
SCN
= 1,2.10
-2
M
Fe
3+
+ 3SCN
-
= Fe(SCN)
3
khi C
SCN
= 4.10
-2
M
Fe
3+
+ 4SCN
-
= Fe(SCN)
4
-
khi C
SCN
= 1,6.10
-1
M
Fe
3+
+ 5SCN
-
= Fe(SCN)
5
2-
khi C
SCN
= 7.10
-1
M
Theo nng ca thuc th mu sc ca phc bn i t mu vng sang mu
. Trng hp ny phi cho lng thuc th nh nhau dung dch kho st v
dung dtch tiu chun.
- pH mi trng phi n nh mt gi tr nht nh bi v cc ion kim loi
trong dung dch phi chu s thu phn.
M
m+
+ H
2
O M
(m-1)+
+ H
+

M
(m-1)+
+ H
2
O M
(m-2)+
+ H
+

V d: Phc Fe
3+
vi Salisalat.
pH < 4 to phc mu tm c dng Fesal
+

O pH t 4-9 to phc mu c dng Fesal
2
-

pH > 9 to phcc mu vng c dng Fesal
3
3-

- Phc mu phi bn vi trong thi gian nht nh kp o mt quang.
Thi gian t 5 - 20'l tt nht.








Thi gian o t Thi gian o t
D = f(t) D = f(t)
Nu phc km bn c th dng thang mu gi v c cng mu ging
dung dch kho st nh: mu vng cam dng K
2
Cr
2
O
7

8.2.3. Ph hp th v chn knh lc.
8.2.3.1. Ph hp th.
Theo nh lut Bouger Lambert Beer tac:

77
l C D . .

E =
Khi C=1mol/l, l=1cm th D=

E
Vy

E l mt quang ca lp dung dch 1cm vi nng 1mol/l.

E : L i lng c trng cho kh nng hp th nh sng n sc ca cht mu,

h s tt phn t ph thuc vo bn cht ca cht mu trong dung dch v bc
sng nh sng chiu vo, cht mu c kh nng hp th nh sng cng ln c h s
tt phn t cng ln. Thc nghim xc nh vi nhiu hp cht mu thy

E khng > 2.10

5
.
thy r s ph thuc ca E vo nh sng chiu vo ta xem ng biu
din s ph thuc
) (
f D =

f = E

Hnh 8.2 Ph hp th ca hai cht A v B
Qua dng ng cong c nhiu max, vi mt quang ln nht. Nh
vy nh sng c mu ng vi bc sng max th dung dch hp th nh sng ti
ca cht mu l ln nht E max.
Vic s dng E max chnh l nguyn nhn dng ph hp th xc nh
nh tnh, nh lng cc cht.
8.2.3.2. Knh lc mu:
Cch chn knh lc nu xc nh c quang ph hp th ca dung dch
nghin cu, ngi ta c th chn c knh lc mu thch hp ch cho qua nhng
tia sng no m dung dch c hp th v gi li cc tia cn li.
Nh vy mu ca knh lc trng mu ph vi mu dung dch, tc l cc tiu
ca knh lc trng cc i hp th ca dung dch mu.
8.2.4. Cc phng php so mu

78
8.2.4.1. Phng php so mu bng mt.
Nguyn tc: Mt c kh nng nh gi mc bng nhau ca hai cng
sng, nn thc ra phng php so mu bng mt l lm cho cng hai chm
sng (i qua dung dch phn tch v dung dch tiu chun) bng nhau. Phng php
c chnh xc khng cao nhung n gin, d lm, nhanh.
C cc phng php chnh.
- . Phng php dy tiu chun.
+ To dy tiu chun:
Ly 10 n 12 ng nghim ng nht cho vo dung dch tiu chun ca
ion cn xc nh vi lng tng dn. Sau thm dung dch thuc th v cc cht
cn thit to mu khc, ri cho thm n th tch bng nhau c dy tiu chun c
cng mu tng ln.
Xc nh: Ly mt ng nghim khc (ging ng tiu chun).
Lm tng t dy tiu chun, so snh mu dy tiu chun, mu ng no
ging ng dy tiu chun c nng ng ng tiu chun , nu mu trung gian
hai ng ly trung bnh cng.
V d: Xc nh pH ca t:
Cch tin hnh ly 5g t nghin. Ry vo bnh tam gic thm vo 5 g
KCl 0,1N pha keo sau ht dung dch thm 3ml dung dch ch th to mu em
so vi dy tiu chun pH. Xc nh c gi tr pH.
- . Phng php pha long v chun so mu.
8.2.4.2 Phng php so mu bng my.
Thng dng my so mu quang in o chnh xc mt quang ca
dung dch cht mu, ri t mt quang c suy ra hm lng cht cn phn tch,
hoc biu th mt quang v cng dung dch tiu chun trn th to dy
tiu chun. Ri t suy ra cht cn xc nh. th khng qua gc to v dung
dch cn ion l, dung dch khng hon ton tinh khit.









79
1.0 -

hp th, D *

0.8 -
*


0.6 -
*


0.4 -

*

0.2 -

*
* C max Nng phn tch (mN)
0.0 + + + +
0.0 0.5 1.0 1.5 2.0
Hnh 8.3 S ph thuc nng cht nghin cu vo mt quang.
8.3. Phng php sc k
8.3.1. Khi nim v phng php:
1903, nh bc hc Nga Xvet a ra mt phng phap mi tch cc hn hp
cc cu t ring bit. ng cho mt hn hp sc t thc vt i qua ct cha CaCO
3
,
cc sc t khc nhau c gi li trn nhng lp khc nhau ca ct hp ph. Theo
Xvet th khi cho mt dung dch sc t qua ct hp ph, cc cu t c chia thnh
nhng lp mu, lp ny trn lp kia cng nh tua sng trong quang ph, nh xc
nh c nh tnh v nh lng hn hp cc cu t. T phng php sc k ra
i v ngy nay cng c ng dng rng ri dng tch hn hp phc tp, xc
nh tinh khit ca ho cht, thu hi ho cht qu
Phn loi phng php: Chia thnh 4 loi:
1- Sc k hp ph phn t.
2- Sc k kt ta.
3- Sc k phn b hay sc k giy.
4- Sc k trao i ion.
8.3.2. Phng php sc k trao i ion:

80
8.3.2.1. Nguyn tc:
Da trn phn ng trao i thun nghch gia cc ion trong dung dch phn tch
vi ion linh ng ca nha trao i (Ionit).
Cc Ionit thng dng:
Cationit: C kh nng hp th trao i cc Cation.
Anionit: C kh nng hp ph trao i cc Anion.
V d: Dung dch phn tch c Cation A
+
khi cho tip xc vi Cationit Bi
+
s phn
ng:
A
+
+ Bi
+
Ai
+
+ B
+

Kt qu A
+
s thay th v tr Bi
+
trong Ionit.
Cn bng phn ng c thit lp:
| || |
| || |
+ +
+ +
=
Bi A
B Ai
B A
K
/

[Ai
+
][A
+
] nng cn bng ca ion A
+
trong Ionit v dung dch.
[Bi
+
][B
+
] nng cn bng ca ion B
+
trong Ionit v dung dch.
K
A/B
c th o bng thc nghim. Nu:
K
A/B
= 1 khng c s hp th chn lc.
K
A/B
> 1 Ionit hp th ion A
+
mnh hn ion B
+
K
A/B
< 1 Ionit hp th ion B
+
mnh hn ion A
+

Hng s chn lc ph thuc vo nhiu yu t nh: Bn cht Ionit, bn cht ion cn
phn tch, iu kin tin hnh nh nng , nhit , pH ca dung dch do vy
cn phi chn Ionit thch hp.
Phn loi Ionit:
Cc Ionit thng c hai loi: Ionit v c nh Pemitit
(mNa
2
O.nAl
2
O
3
.pSiO
3
.xH
2
O), cc Ionit hu c nh sunfophenol focmandehyt.
Thng cc Ionit hu c bn hn v c hot tnh ho hc cao hn.
8.3.2.2. Cch tin hnh sc k trao i ion.
Nha trao i ion c ngm trong nc ct, ra sch v c chuyn sang dng
cha ion trao i bng dung dch 0,01M 1M ca ion trao i. Sau nhiu ln ra
bng dung mi ra, nha c np thm ct sc k. Dung dch cn phn tch c
a ln phn trn ca ct v y xy ra qu trnh hp th. Sau dng dng dch
ra c nng khng i hay c nng thay i tch cc ion ra khi nhau.
8.3.3. Phng php sc k phn b:
8.3.3.1. Nguyn tc:

81
Sc k phn b l phng php tch cht c trong hn hp cn tch da vo tnh
cht phn b ca chng gia hai dung mi tnh v dung mi ng lun tip xc
vi nhau.
S phn b cc cht cn xc nh gia 2 dung mi c c trng bi h s phn
b K
f
:

d
t
f
C
C
K =
Nu C
t
l nng cht phn tch trong tng tnh.
C
d
l nng cht phn tch tng ng.
K
f
l h s phn b ca cht cn phn tch hai tng.
Khi qu trnh t n cn bng K
f
bng ch ph thuc vo bn cht ca cht
cn xc nh, dung mt v nhit .
Tu theo k thut tin hnh ngi ta chia phng php sc k phn b thnh 2
loi:
- Sc k phn b trn ct.
- Sc k phn b trn giy.
8.3.3.2. Sc k phn b trn giy.
Cht mang l mang l giy sc k (l loi giy lc c bit, tinh khit, mn)
c tin hnh:
Chm dung dch cc cu t cn tch ln giy sc k, phi kh ri nhng vo dung
mi thch hp, dung mi ny di chuyn trn giy theo th ca giy v ko theo s di
chuyn ca cc cu t cn tch. trnh s bay hi phi tin hnh phn tch trong
cc bnh thu tinh hay hp pettri.
Trong qu trnh sc k mi mt cht c h s K
f
khc nhau, s chuyn nh vi vn
tc khc nhau, cu t no c h s K
f
cng nh chuyn nh cng nhanh.
Da vo qung ng i ta xc nh c tha s chm R
f
:
R
f
=

L
1
: Khong cch di chuyn ca cu t cn phn tch
L
2
: Khong cch di chuyn ca dung mi
Gi tr R
f
khng ph thuc vo nng cc cu t c trong dung dch, ch ph
thuc vo dung mi, tnh cht ca giy sc k v bn cht ca cu t. V vy R
f
l
mt i lng khng i v c trng cho mi mt cu t. R
f
ca mi mt cu t
c xc nh bng thc nghim, da vo c th xc nh nh tnh cc cu t.
V d: ion Cr
3+
Al
3+
Fe
3+
Zn
2+

82
R
f
0,1 0,18 0,40 0,86
Phng php sc k trn giy l mt phng php tch vi lng rt thun li trong
phn tch cc cht hu c c tnh cht gn ging nhau nh: cc axit amin, peptit





























83
Chng 9
SAI S TRONG HO PHN TCH

9.1. Sai s - Phn loi sai s - Biu din sai s
9.1.1: Sai s:
Khi tin hnh xc nh mt cht no th thng thng phi thc hin mt lot
php xc nh. Php xc nh coi nh l chnh xc khi kt qu gn nhau v gn vi
gi tr thc ca cht nghin cu.
Trong thc t phn tch bao gi cng c sai s. Sai s l hiu gia kt qu thu
c v gi tr thc. Khi phn tch bao gi cng gp phi sai s, ngay c trong qu
trnh phn tch cn thn nht. C nhiu nguyn nhn gy ra sai s, vic nghin cu
sai s gip cho ngi phn tch nh gi ng kt qu phn tch v t c bin
php x l theo tng nguyn nhn mt.
9.1.2: Phn loi sai s:
c chia 3 loi:
- Sai s ngu nhin
- Sai s h thng
- Sai s th
9.1.2.1. Sai s ngu nhin: l nhng sai s gy nn bi nhng nguyn nhn khng
c nh v khng bit trc. Sai s ngu nhin c th do nguyn nhn khch quan
(nhit thay i, kh quyn khng sch. . . ) nguyn nhn ch quan (s cm nhn
ca mt ngi phn tch khi quan st, c kt qu. . . )
Sai s loi ny rt nh, khng c quy lut, thng gp trong khi tin hnh
nhng bc phn tch, ta khng th loi tr c sai s ngu nhin m ch
hn ch sai s ny thng qua vic tng s ln phn tch v dng phng php
thng k ton hc x l kt qu phn tch.
9.1.2.2. Sai s h thng: l nhng sai s do cc nguyn nhn c nh gy ra, sai s
h thng c th do bn phn phng php phn tch khng chnh xc, dng c o
lng (pipet, bnh o, cn. . .) khng ng, ho cht khng tinh khit, nng
dung dch chun khng chnh xc, ngi phn tch thiu kinh nghim. . .
Loi sai s ny cho kt qu thng ln hn hoc nh hn gi tr thc, thng
chia 3 nhm:
Sai s h thng do phng php: do phng php khng chnh xc
(v d: trong qu trnh phn tch lc ra kim tra khng sch, lng
kim tra chuyn khng hon ton. . . v vy cn phi chn phng
php no cho ti u nht).

84
Sai s h thng do dng c, ho cht: do pipet c sai s ln cn sai,
my o khng chnh xc, ha cht khng sch, dung dch c nng
khng ng. . .
loi sai s ny cn iu chnh dng c, xc nh sai s ca pipet,
buret, xc nh li nng . . .
Sai s h thng do c bit: sai s ny do ngi phn tch gy nn, do
thiu kinh nghim, thin v khi quan st, phn bit loi mu khng
chnh xc. . . sai s ny thng km theo vi sai s th.
9.1.2.3. Sai s th:
Sai s ny thng l ln, khng c quy lut, nh hng nng n kt qu cui
cng.
Nguyn nhn do ngi phn tch khng thc hin ng quy trnh phn tch,
lm cu th, nhm ln, chn phng php phn tch khng cho kt qu n nh, tnh
ton nhm ln.
loi b sai s ny thng lm vic cn thn, lm ng quy trnh, lm
nhiu ln ly kt qu trung bnh.
9.1.3. Cch tnh ton sai s:
Gi s c mt i lng no c xc nh nhiu ln c cc gi tr tng
ng x
1
, x
2
, . . . , x
n
v c gi tr trung bnh l
n
x
x
n
i
i
=
=
2

Gi tr x
i
thng khc so vi gi tr thc , hiu s gia x v c gi l sai
s, tu theo cch biu din sai s ta phn thnh sai s tuyt i v sai s tng i.
9.1.3.1. Sai s tuyt i:
Mt i lng c gi tr thc em xc nh nhiu ln c cc gi tr x
1
, x
2
, . .
. , x
n
sai s tuyt i ca mi ln l:
=
i i
x d (9.1)
l gi tr thc, tu thuc ln nh ca x
i
ta c gi tr m hay dng.
Thng thng gi tr thc khng bit trc nn sai s tuyt i khng tnh
c, nu thay bng gi tr trung bnh x . Ta c lch ca mi ln xc
nh l:
x x b
i i
= (9.2)
n
x
x
n
i
i
=
=
2


85
lch ca mi ln xc nh l:
x x b
i i
=
Nu dng sai s tuyt i nh gi khng bit c chnh xc ca php
xc nh. V d: hm lng thc ca nguyn t A l 45,2mg ca nguyn t B l
215,0mg nh vy sai s tuyt i ca 2 php o l 0,6mg. Vy r rng php xc
nh ca B chnh xc hn v o 216,0mg cha sai s 0,6mg, bit c mc
chnh xc ngi ta dng khi nim sai s tng i.
9.1.3.2.Sai s tng i:
Nu chia sai s tuyt i cho gi tr thc ca cht cn xc nh ta s c sai s
tng i. Nu gi e l sai s tng i, thng sai s c biu din theo %) ta c:
100 . %

i
d
e = (9.3)
Trng hp cha bit trc
100 . %
x
b
e = (9.4)

n
b
b
n
i
i
=
=
2
lch trung bnh

n
x
x
n
i
i
=
=
2

9.1.4. L thuyt tng qut ca sai s:
Vic tnh ton sai s tuyt i v tng i theo cc biu thc trn ch p dng
cho tng cng on phn tch, trong thc t quy trnh phn tch bao gm nhiu cng
on lin tip. Sai s phn tch chnh l t hp ca tt c cc sai s ca tng cng
on.
Gi thit ca cng on cho cc i lng o x
1
, x
2
, . . . , x
n
chu sai s tuyt i
n
x x x
d d d ..., ,
2 1
v sai s tng i
n
x x x
e e e ..., ,
2 1
v y l i lng t hp ca cc php o
( )
n
x x x f y ..., ,
2 1
=
Sai s tuyt i ca y l d
y
:

n
x
n
x x y
d
x
y
d
x
y
d
x
y
d . ... . .
2 1
2 1
|
|
.
|

\
|
c
c
+ +
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=
Sai s tng i e ca y l e
y
:

n
x
n
x x y
d
x
eny
d
x
eny
d
x
eny
e . ... . .
2 1
2 1
|
|
.
|

\
|
c
c
+ +
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=

86
T ta c th thy :
Nu t hp l cng hoc tr :
2 1
x x y = do
2 1
x x y
d d d + =
y
d
e
y
y
=
Nu t hp l tch vi mt hng s :
x
d
a
d a
y
d
e e d a d x a y
x
x
x
y
x y x y
= = = = = =
.
, . , .
Nu t hp l tch hoc thng ca cc i lng x
1
, x
2
,. . . ;
2 1
.x x y = th
y e d
y y
. =
2 1 2 1
1
2 1
2
1 2
2 1
2 1 2 1
2 1
2 1
.
.
.
.
. .
. .
x
d
x
d
x x
d x
x x
d x
y
d
e
d x d x d
d
x
y
d
x
y
d
x x x x y
y
x x y
x x y
+ = + = =
+ =
+ =

2 1
x x y
e e e + =
=
2
1
x
x
y tng t :
2 1
x x y
e e e =
2 1
2
1 2
2
1
2
1
2
2
2
1
2
2 1
2 1 2 1
2
1
2 1
.
.
.
.
.
1
. .
x
d
x
d
x
x
x
d x
x
x
x
d
y
d
x
d x
d
x
d
d
x
y
d
x
y
d
x x x x y
x
z y
x x y
= =
=
+ =

2 1
x x y
e e e =
Nu t hp l tham s lu tha:
n
x y =
x
d
n
x
d x n
y
d
d x n d
x
n
x
x
y
x
x
y
.
. .
. .
1
1
= =
=

x y
e n e . =

87
V d : Khi cn mt mu vt, u tin ta cn b c 19,0712g (x
1
) sau
cn b v mu c 19,5034g (x
2
) hi sai s ca php cn, nu bit chnh xc
ca cn b l 0,2mg.
Gii:
Gi vt cn c khi lng l y th

( )
( )
% 1 , 0
2 , 432
10 . 4 , 0
%
4 , 0 2 , 0 2 , 0
2 , 432 0712 , 19 5034 , 19
2
1 2
2 1
~ = =
= + = + =
~ = =
y
d
e
mg mg d d d
g g x x y
y
x x y

9.2. chnh xc, hi t v tin cy
y l 3 tiu ch nh gi kt qu phn tch
9.2.1. chnh xc :
Phn tch chnh xc khi kt qu thu c trng vi gi tr thc. S sai lch gia
kt qu phn tch v gi tr thc biu din chnh xc ca php phn tch, gi tr
ny cng nh th chnh xc cng cao. Thng thng sai s tng i nh gi
chnh xc ca php phn tch, sai s tng i cng nh th chnh xc cng
cao.
9.2.2. hi t :
Khi tin hnh phn tch thng phi lm nhiu ln cc kt qu thu c
thng khc nhau v c gi tr l chnh lch b. Khong gi tr m xi phn c
gi l hi t, khong cng nh hi t cao (ch mc sai s ngu nhin)
khong cng ln hi t nh ( phn tn cao - ngoi sai s ngu nhin cn c
sai s Th. . . )
9.2.3. tin cy :
Php phn tch c coi l tin cy khi chnh xc cao hi t cao.
Trong qu trnh phn tch mu khng c trc gi tr thc cho nn ngi ta
thng chn cc phng php c hi t cao cn phng php tuy chnh xc
nhng s lp li nhiu ln vn gy sai s cho php phn tch.
chnh xc, hi t, tin cy, ng dng xc nh s ln phn tch.
Nu ta thy hi t cao s ln lm th nghim nhc li t, cn phn tn
cao ( hi t nh) s ln nhc phi nhiu.
Ngoi cc loi sai s trn ngi ta cn dng phng php thng k ton hc
xc nh sai s ngu nhin.
9.3. Tnh ton sai s h thng

88
Trong 3 loi sai s th sai s h thng c th tnh c v c th c s dng
kim tra phng php phn tch hoc chnh l kt qu phn tch.
Trong phng php ho hc, phng php dng c thng s dng cc phn
ng ho hc thch hp tch hoc chuyn ho cht cn phn tch, song do cc
phn ng ny khng bao gi hon ton nn c nh hng n chnh xc ca
php phn tch, cn nhiu nguyn nhn gy ra phn ng khng hon ton nhng
y ch quan tm n 2 nguyn nhn chnh:
- Do s cn bng phn ng ho hc (nguyn nhn ch quan)
- Do ch th phn ng khng ng im tng ng (nguyn nhn khch quan)
9.3.1 Sai s h thng do cn bng phn ng ho hc gy nn :
V d : phn ng gia 2 cht A (cht cn phn tch) v cht B (thuc th)
A + n B ABn
Hng s cn bng ca phn ng:

| |
| || |
n
B A
ABn
K
.
=
Trong qu trnh chun sau im tng ng cn d mt lng cht A
cha tham gia phn ng y chnh l ngun sai s cho phng php
| |
| |
| | K B
ABn
A
n
1
. = (*)
Nu gi C
A
nng cht A d ti im cn bng
| | | | ABn A C
A
+ =
| | | | A C ABn
A
= thay vo (*) c:
| |
| | ( )
| | K B
A C
A
n
A
.

= nu coi [A]<<C
A
. c:
| |
| | K B
C
A
n
A
.
= nu sai s tng i ca phng php l:

| |
| | K B C
A
e
n
A
.
100
100 . % = = (9.5)
Nu gi nng cht A cha phn tch l COA, th tch dung dch ban u
l VO v th tch dung dch lc t cn bng l Vcb sai s tng i cn c biu
din

| |
100 .
.
.
%
O OA
cb
V C
V A
e =

89
Qua 2 biu thc ta thy mun phn ng xy ra hon ton hay sai s nh
nht cho php ch cn c K ln, hay [B] ln (tc thuc th d), nu phn ng to
kt ta ABn thay T K = ta c

K
T
1
=

| |
n
B
T
e
100 .
% = (9.6)
9.3.2. Sai s h thng do ch th gy ra :
Trong qu trnh phn ng thng dng ch th pht hin im tng
ng nhng ch th khng bao gi bo hiu ng im tng ng, thng im
kt thc khc im tng ng nn gy sai s do ch th gy ra.
Sai s ch th c th c tnh theo cng thc sau:

( )
100 . %
BTD
BTD B
V
V V
e

= vi
B
A A
BTD
N
N V
V
.
= (9.7)
V
B
: th tch dung dch tiu chun B dng khi chun
V
BTD
: th tch dung dch tiu chun B cn t im tng ng
V
A
: th tch dung dch cht cn phn tch A
N
A
, N
B
: nng dung dch tiu chunB v cht cn xc nh A
Vic tnh ton sai s c tin hnh theo cc bc sau:
Bc 1: T ch th dng tnh cc gi tr pH, E, pX. . . ti im kt thc chun
: (pT
KT
: pH
KT
, E
KT
, pX
KT
. . . )
pT: l gi tr pH, E, pX. . . m ti thi im cht ch th mu pht tn hiu l r
nht.
Bc 2: T phn ng chun tnh gi tr pH
T
, E
T
, pX
T
. . .
Bc 3: So snh pT
KT
vi pH
T
, E
T
, px
T
. . . chn biu thc tnh V
B
.
Bc 4: t biu thc chn tnh th tch dung dch dng trong qu trnh chun
v tnh sai s.
V d 1: Khi chun 20ml NH
4
OH 0,1N bng KCl 0,1N dng metyl
(pK
a
=5) lm ch th, tnh sai s chun cho pK
b
=4,75
Gii:
Bc 1: Ta dng chun khi dung dch t mu vng sang tc gi tr:
1 5 1 . = =
a
K p pH
6 =
KT
pH hay 4 =
KT
pH

90
Bc 2: Tnh pH
T
:

4 , 5
. lg .
2
1
. .
2
1
7
'
~
=
T
i mu b T
pH
C K p pH

Bc 3: So snh ta c:
T KT
pH pH > = 6 tc kt thc chun trc im tng ng mc sai s m
T KT
pH pH < = 4 tc kt thc chun sau im tng ng mc sai s dng
Bc 4: Tnh sai s:
*Ti 6 = pH :
Do kt thc trc im tng ng nn dung dch d NH
4
OH, pH dung dch do
h amni quyt nh:

| |
| |
| |
| |
% 055 , 0 100 .
20
20
1 10 . 5 , 5
20
%
1 10 . 5 , 5
20
1 0 1 . 5 . 5
20
10 1
20
26 , 3 1
20
. lg
1
1 , 0 .
1 , 0 . 20
. lg 26 , 9 6
1
.
.
. lg 26 , 9 6
. .
.
. lg 75 , 4 14
. lg . 14 . lg .
4
4
4
10 . 5 , 5
26 , 3
4
4
4
4
4
4 4
4 4
=

+
=
+
= + =
=
|
|
.
|

\
|
+
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

=
= =

e
V
V
V V
V
N V
N V
N V N V
N V
pH
OH NH
Cl NH
K p
OH NH
Cl NH
K p pH
HCl
HCl
HCl HCl
HCl
HCl HC
OH NH OH NH
HCl HCl OHl NH OH NH
HCl HCl
b a


Ti 4 = pH :
Do kt thc chun sau im tng ng dung dch d HCl nn pH dung
dch do HCl quyt nh:

OH NH HCl
OH NH OH NH HCl HCl
V V
N V N V
4
4 4
. .
. lg 4
+

=
Thay s:

91

( )
( )
( ) ( )
( )
( )
( )
( )
% 02 , 0 100 . 20 : 20
1 10
10 1 . 20
%
1 10
10 1 . 20
10 1 . 20 1 10 .
10 1 . 20 . 10
20 20 . 10 10
20
20
10
20
1 , 0 . 20 1 , 0 .
20
1 , 0 . 20 1 , 0 .
. lg 4
3
3
3
3
3 3
3 3
3 3
4
+ =
(

+
=

+
=
+ =
+ =
+ = =
+

=
+

e
V
V
V V
V V
V
V
V
V
V
V
HCl
HCl
HCl HCl
HCl HCl
HCl
HCl
HCl
HCl
HCl
HCl

V d 2: Chun 20ml Fe
2+
0,1N bng K
2
Cr
2
O
7
0,1N trong mi trng axit
| | ( ) 1 =
+
H ch th ifenylamin ( ) Indkh e Indox = + 2 . Tnh sai s chun , do ch th
gy ra:

v E
v E
v E
ifenyla
Cr
O Cr K
Fe
Fe
76 , 0
33 , 1
77 , 0
0
min
0
2
0
3
7 2 2
2
3
=
=
=
+
+
+

Gii:
Bc 1: Tnh E kt thc ta dng chun khi dung dch t mu xanh sang mu
tm than, tc 2 gi tr:

v E
v E
E
KT
KT
KT
73 , 0
79 , 0
03 , 0 76 , 0
2
059 , 0
76 , 0
=
=
= =

Bc 2: Tnh E
T
:

| || |
| | | |
y x
Fe
O Cr
Fe
Fe
T
kh kh
ox ox
E E
E
2 1
2 1
0 0
.
.
. lg . 059 , 0
7
. 6
2
7 2
2
3
+
+
=
+

+
+

Thay s vo tnh c:
476 , 1 =
T
E
Bc 3: So snh E
KT
vi E
T
ta thy c 2 gi tr E
KT
u nh hn E
T
nh vy
chun kt thc trc im tng ng (d Fe
2+
). Sai s m vy E
dd
c tnh
theo cp
+
+
2
3
Fe
Fe
E d.

92
Bc 4:
Ti v E 79 , 0 = :
% 4 , 31 100 .
20
20
10 1
10 . 20
%
10 1
10 . 20
10 1
10 . 20
10
20
059 . 0
020 . 0
20
. lg
020 , 0 77 , 0 79 , 0
20
. lg . 059 , 0
20
. lg . 059 , 0 77 , 0 79 , 0
1 , 0 . 1 , 0 . 20
1 , 0 .
. lg . 059 , 0 77 , 0 79 , 0
. .
.
. lg . 059 , 0
39 , 0
39 , 0
39 , 0
39 , 0
059 , 0
020 , 0
0
059 , 0
020 , 0
059 , 0
020 , 0
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2
7 2 2 7 2 2
2 2
7 2 2 7 2 2
2
3
=

+
=
+
=
+
=
=

= =

+ =

+ =

+ =
+ +
+
+
e
V
V
V
V
V
V
V
V
V
V
V
V V N V
V V
E E
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K
O Cr K O Cr K
Fe
O Cr K O Cr K
Fe
Fe
Fe

Ti v E 73 , 0 = :
Tnh tng t ta c % 8 , 81 % = e Sai s do ch th kh ln v vy mun dng ch
th ny cn phi gim
+
+
2
3
Fe
Fe
E bng cch cho thm H
3
PO
4
lm gim | |
+ 3
Fe v in
th dung dch gim.
V d 3: C 50ml dung dch cha Cl
-
, cho vo 0,55ml K
2
Cr
2
O
7
0,1N v chun
xc nh Cl
-
bng 5ml AgNO
3
0,01N. Hy tnh sai s chun do ch th gy ra
cho:
12 10
10 , 10
4 2

= =
CrO Ag AgCl
T T
Gii:
Bc 1: Tnh pCl
KT
:
| | M CrO
3 2
4
10
5 55 , 0 50
1 , 0 . 55 , 0

=
+ +
= . Suy ra | |
+
Ag cn kt ta Ag
2
CrO
4
l:

| |
| |
5 , 5 ; 5 , 4
10
5 , 4
2
4
4 2
= =
= =

+
KT
CrO Ag
pCl pAg
M
CrO
T
Ag

Bc 2: pCl
T


93
5 . lg = =
AgCl T
T pCl
Bc 3: So snh:

T KT
pCl pCl > kt thc chun sau im tng ng
Bc 4: tnh sai s do kt thc sau im tng ng nn pCl c tnh theo lg
Ag
+
d:

+
+ +
+

=
Cl Ag
Cl Cl Ag Ag
V V
N V N V
pAg
. .
. lg
Do bi cho Vdung dch cn xc nh l 50ml m y phi tnh nng :

N N
V
Cl
Cl
4
10 . 65 ; 9
50 5
. 50 01 , 0 . 5
. lg 5 , 4

=
+

Sai s c tnh:
% 62 , 3 100 .
10 . 65 , 9 . 50
10 . 65 , 9 . 50 01 , 0 . 5
100 .
.
. .
%
4
4
=

+ +
Cl Cl
Cl Cl Ag Ag
N V
N V N V
e


















94



TI LIU THAM KHO:




[1] Nguyn Tinh Dung. Ho Phn tch, phn III: Cc phng php nh
lng ho hc, NXB Gio dc, H Ni (2000).
[2] Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ho hc Phn tch,
NXB Khoa hc v k thut (2002).
[3] V Th Bch Hu. Ho Phn tch. NXB Gio dc, H Ni (2007).
[4] Nguyn Trng Sn, Hong Xun Lc. Gio trnh Ho V c Phn tch,
NXB i hc v gio dc chuyn nghip, H Ni (1991).
[5] Phan Th Hong Oanh, Trn Ngc Tuyn, Nguyn Ph Huyn Chu,
Nguyn Vn Ly, Nguyn Vn Hp. Bi ging thc tp Ho V c Phn tch
(2004)