Giáo Án Hóa Phân Tích

HA PHN TCH
(H, 30t)
Phn 1. Cn bng ion trong dung d!h n"#!
1. $i !"%ng &' ho( )hn t*!h
1.1. +i#i thi,u &' h-. )hn t*!h
Khng c phn tch th khng th c tng hp
Fr. Engels
Khai nim: hoa phn tich la mn khoa hc v cac phng phap xac nh thanh phn
nh tinh va nh long cua cac cht va hn hop cua chung.
Hoa phn tich thong oc chia thanh hai phn Hoa phn tich nh tinh va hoa phn
tich nh long. Hoa phn tich nh tinh bao gm cac phng phap phat hin, nhn bit
cht va thanh phn cu tao cua cht. Hoa phn tich nh long gm cac phng phap xac
nh ham long cua cht va cac thanh phn cu tao cua no.
Phn loai cac phng phap dung trong hoa phn tich:
- Phng phap phn tich hoa hc: dua trn cac phan ung hoa hc (phan ung phn
tich) va nhung dung cu n gian.
- Phng phap phn tich vt li: su dung may moc phuc tap o hoc ghi lai nhung
hin tong vt ly nh cong vach quang phat xa nguyn tu, cong phn r phong
xa hat nhn nguyn tu, .
- Phng phap phn tich hoa li: kt hop cac phan ung hoa hc voi cac tinh cht hoa
li cua h tao nn tin hiu phn tich ri dung may moc thit b ghi lai nhm phn tich
nh tinh, nh long cht cn phn tich.
Cac phng phap thuc nhom thu 2 va 3 con oc gi la cac phng phap phn tich
cng cu.
1./. 0.i tr1 &2 3ng d4ng !5. h-. )hn t*!h
Hoa hc phn tich ong vai tro quan trng trong su phat trin cua cac mn hoa hc
khac cung nh cac nganh khoa hc khac nhau, cac linh vuc khac nhau cua cng ngh, san
xut, oi sng x hi.
Vi du:
- Trong y hc: hoa phn tich la c so cua cac phep thu lm san, giup cho cac bac si
chn oan chinh xac oc bnh. Vi du ngoi b bnh tiu ong nu long ong ngu
nhin trong mau bng hoc cao hn 200 mg/dl.
- Trong cng nghip hoa phn tich: la phng tin giup thu nghim cac loai nguyn
liu va kim soat c thanh phn hoa hc va cht long san phm.
- Trong vic bao v mi trong: hoa phn tich giup xac nh tac nhn gy nhim
tu o co cach xu ly.
- Trong dinh dng: hoa phn tich xac nh cac thanh phn trong thuc phm, ca
thanh phn co ich cung nh cht co hai cho suc khoe, tu o giup xac nh gia tr dinh
dng cua thuc phm. Vi du: xac nh long cht c lu huynh va sunIite trong mu
mng kh; histamine (o nng thp vn gy ngua ngay, d ung; cao hn thi gy ng c
va co th dn n tu vong) trong ca thu, ca ngu,
/. C(! 6h(i ni,7 !% b8n trong dung d!h !h9t :i,n ;<
/.1. => thu<?t @A :i,n ;< B C :i,n ;<
Thuyt !n ly "renut #n$% &''()*
- Khi hoa tan mui, acid, bazo trong noc thi phn tu cua chung b phn li thanh cac
hat mang in tich trai du (ion m va dng).
- Tinh cht dn in cua cac dung dch acid, bazo, mui trong noc ti l voi nng
cac ion trong dung dch
Su in ly la qua trinh phn tu trong mt dung mi phn ly thanh ion.
Cht in ly la cht co kha nng phn li thanh ion khi hoa tan vao noc lam cho
dung dch dn oc in.
Hin tong in ly la kt qua cua su tng tac giua phn tu dung mi phn cuc va
phn tu cht tan. Co nhung hop cht ma lin kt trong phn tu la lin kt cng hoa tr
phn cuc nhng do tac dung phn cuc hoa cua dung mi phn tu cung phn ly thanh
nhung ion, thi du nh HCl H
Cl
-
. Tac dung nay cua dung mi thong oc gi la
t+c ,ung -n h. phn t/.
Da s cac cht in ly la cac hop cht ion. Do tinh cht phn cuc manh, cac phn tu
dung mi but cac ion ra khoi mang loi tinh th va khuch tan chung trong toan b dung
dch. Tac dung nay cua dung mi gi la t+c ,0ng phn ly c+c -n.
Do tinh cht nh hong cua cac lng cuc nn giua cac ion va cac phn tu dung
mi co tac dung hut. Tac dung nay dn n su hinh thanh tp hop cac phn tu dung mi
quanh cac ion. Tp hop nay gi chung la cac s-n1.t hay i voi dung mi la noc gi la
hr.t #.2).Tac dung nay cua dung mi gi la t+c ,0ng s-n1.t h. c+c -n.
Na
Cl
-
noc Na
aq
Cl
-
aq
DA :i,n ;< !5. n"#!E
Mc du voi dn in rt nho nhung noc nguyn cht cung co kha nng dn in.
Diu o co nghia la trong noc nguyn cht cung co cac ion mang in tich. Cac ion nay
oc tao thanh do su in ly cua noc theo phng trinh:
2H
2
O H
3
O
OH
-
Hin tong nay (noc vua ong vai tro la dung mi, vua la cht in ly) gi la s3 t3
!n l.
C :i,n ;< FE
u s phn tu b in ly / tng s phn tu hoa tan
0 u _ 1
Cht in ly oc chia ra thanh cht in ly manh (NaOH, NaCl, HCl, ... voi u ~
30, cht in ly yu (H
2
CO
3
, CH
3
COOH, ...) voi u 3.
Tu gia tr u ngoi ta tam phn loai:
u _ 2: Cht in ly yu (cac axit yu, cac baz yu).
2 _ u _ 30: Cht in ly trung binh (HF, H
2
SO
3
o nc 1).
u _ 30: Cht in ly manh cac axit manh, cac baz manh, cac mui trung tinh.
D in ly phu thuc vao:
- dung mi: dung mi cang phn cuc, trong nhung iu kin nh nhau, in ly
cang lon.
- nhit : qua trinh in ly co hiu ung nhit nn anh hong cua nhit co th xet
theo quy tc Le Chatelier: nu qua trinh in ly la qua trinh thu nhit thi khi nhit tng
in ly tng va ngoc lai.
- nng dung dch: cung theo qui tc Le Chatelier: khi pha long dung dch cht
in ly bng noc s lam tng long phn tu phn li, tuc la in ly tng khi pha long
dung dch.
/./. Cn bng trong dung d!h !h9t :i,n ;< <?u B Hng @G )hn ;i (:i,n ;i) H
Trong dung dch cht in ly yu cac phn khng in ly nm trong cn bng ng
voi cac ion cua chung:
AB A
B
-
Theo nh lut tac dung khi long ta co:
[ ] [ ]
[ ] "4
4 "
K
+
Trong o K la hng s cn bng in li.

nh ;uIt )h. ;oJng K@tL.;d (Mt&.n)E
Gi C, u ln lot la nng mol va in ly cua cht in ly AB. Nh vy ta co:
[ ] [ ]
[ ] ( ) ( )
+
1 1
2 2 2
5
5
5
"4
4 "
K
( )

1
2
5 K
Di voi cht in ly yu u 1, ta co th bo qua u o mu s.
5
K
5 K
2
H thuc nay cho thy dung dch cang long thi in ly cang lon.
/.3. NNng :C &2 ho$t :C
NNng :CE la ai long dung chi ham long mt cu tu (phn tu, ion) trong dung
dch.
Cac cach biu din nng cht tan trong dung dch:
nng th tich cua mt cht long la ti s th tich cua cht long o va th tich cua
dung mi;
mt nng mol:
nng ng long:
nng phn trm (khi long, th tich):
Ho$t :CE i voi cht in ly manh
Cho phan ung: Aa bB cC dD
Hng s cn bng:
[ ] [ ]
[ ] [ ]
6 .
, c
5
4 "
7 5
K
Nhng h thuc nay chi ung khi nng cht nho. Khi nng lon thi phai thay
nng bng hoat a.
Su cn thit v khai nim hoat trong hoa phn tich:
Vi du: HCl H
Cl
-
Di voi cht in ly manh do su phn li hoan toan nn trong dung dch cht in ly
mt ion tng i lon, khoang cach giua chung tng i nho do o luc tng tac tinh
in giua cac ion la ang k, c bit la i voi cac dung dch co nng lon. Theo
Denye va Huckel thi khi o mi ion trong dung dch oc bao quanh boi cac ion khac,
chu yu la cac ion khac du tao thanh mt khi quyn ion` ging nh bu khi quyn bao
quang trai t. Do su hinh thanh lop khi quyn ion o nn hoat ng cua cac ion giam,
anh hong n nhiu tinh cht khac cua dung dch. Chng han, tu su giam tc chuyn
ng cac ion dn n su giam dn in cua dung dch.
D phan anh tinh cht thuc t cua dung dch, i voi dung dch co nng lon ngoi
ta su dung mt ai long oc gi la h-8t 9 . thay cho nng C, voi . : ;.5, trong o
h s chinh li la ;1 oc gi l< h! s= h-8t 9. H s hoat phu thuc vao ban cht cac
ion cn xet va nng cua dung dch. Di voi nng nho: C 0, thi h s hoat
;1.
; phu thuc vao luc ion cua dung dch. Luc ion biu th tng tac tinh in giua
cac ion trong dung dch.
Nu z
1
, z
2
, . la in tich va C
1
, C
2
,. La nng cua cac ion trong dung dch thi:
( )
+ +
n

5 >
5 > 5 >
1
2
2
2
2 1
2
1
2 / 1
... 2 / 1
Nu C 0, 0 thi dung dch rt long, tng tac tinh in khng an k, I1.

Nu 0,02 thi I oc tinh theo cng thuc Debye Huckel:
2
, 0 lg

> ;
Nu 0,02 0,2 thi I oc tinh theo cng thuc:
. . 10 . 33 , 0 1
. , 0 lg
2
6
>
;
+

Trong o b la ban kinh ion ngm noc, cm.
b co gia tr gn ung la: b 3.10 cm.
+

1
. , 0 lg
2
>
;
Nu ~ 0,2 thi I oc tinh theo cng thuc:
4
>
;
+
+

1
. 2 , 0 lg
2
Trong o B la hng s thuc nghim, phu thuc vao ban cht cht in ly.
/.O. nh ;uIt b8o to2n 6hGi ;"Png &#i !h9t :i,n ;i
Di voi cht in ly AB co nng ban u la C va in ly u co cn bng in ly
nh sau:
AB A
B
-
Thi nh lut bao toan khi long co dang:
AB B
-
C
Trong o AB, B
-
ln lot la nng cn bng cua AB va B
-
.
3. Cn bng !5. )h8n 3ng .!id B b.Q
3.1. nh nghR. &' .!id B b.Q
?@nh nghA. .c, 1< 6.> cB. "rrhenus #&''C)
Acid la nhung hop cht ma khi in ly trong dung dch noc cho ion hiro H
.
Vi du: HCl H
Cl
-
Baz la nhung hop cht ma khi in ly trong dung dch noc cho ion hiroxyl.
Vi du: NaOH Na
OH
-
Han ch cua nh nghia acid va baz cua Arrhenius:
- Khng ap dung cho mt s cht hoa tan trong noc cho ra H
hoc OH
-
mc du
trong cng thuc cht nay khng co chua H hoc OH. Vi du: Na
2
CO
3
, Al
2
(SO
)
3
.
CH
3
COONa CH
3
COO
-
Na
CH
3
COO
-
H
2
O CH
3
COOH OH
-
- Khng cho thy su anh hong cua dung mi n tinh cht acid, baz cua cht hoa
tan.
Vi du: HCl la mt acid manh trong dung mi noc, nhng la mt acid yu trong
CH
3
COOH.
?@nh nghA. .c, 1< 6.> cB. 4r-nste, #&DEF)
Acid la mt cht co kha nng cho proton H
.
HA
A
-
(a)
Baz la cht co kha nng nhn proton.
B H
BH
(b)
Cng a b thu oc:
HA B
A
-
BH
acid 1 baz 2 baz 1 acid 2

Mi acid sau khi cho mt proton tro thanh mt baz gi la baz lin hop cua acid o
(HA/A
-
). Va ngoc lai mi mt baz khi nhn mt proton s tao ra mt acid lien hop cua
no (B/ BH
). Mt cp acid baz lin hop oc biu din nh sau:

Acid
Baz
Proton khng co kha nng tn tai o trang thai tu do vi vy mt cht chi th hin r
tinh cht acid hoc baz trong dung mi co kha nng nhn hoc cho proton. Vi du nh
noc la dung mi vua co kha nng cho vua co kha nng nhn proton.
Hay Acid H
2
O
H
3
O
Bazo
on H
3
O
la ion H
b hidrat hoa oc gi la ion hidrono hay oxoni.

Vi du: CH
3
COOH H
2
O
CH
3
COO
-
H
3
O
Cp acid baz lin hop: CH

3
COOH/ CH
3
COO
-
NH
3
H
2
O
NH
OH
-
Theo quan im c in thi NH
khng phai la acid, CN

-
, CH
3
COO
-
khng phai la
baz. Nhng theo thuyt cua Bronsted NH
la acid, CN
-
, CH
3
COO
-
la baz, HCO
3
-
vua la
acid trong cp HCO
3
-
/ CO
3
2-
, vua la baz trong cp H
2
CO
3
/HCO
3
-
, nn HCO
3
-
co tinh cht
lng tinh.
u im cua nh nghia Bronsted:
- Cho thy anh hong cua dung mi n cong acid, baz cua cht tan:
Suc manh cua acid phu thuc vao tinh baz cua dung mi, dung mi co tinh baz
cang manh thi cong cac acid cang cao.
Suc manh cua baz phu thuc vao tinh acid cua dung mi, dung mi co tinh acid
cang manh thi cong baz cang cao.
- Dn gian hoa cach tinh pH, c bit la i voi dung dch mui. Vi mui la hop cht
tao thanh boi acid va baz nn khi tinh pH dung dch mui co th a v dang tinh pH cua
dung dch cac acid, baz.
?@nh nghA. .c, 1< 6.> cB. GeHs
Dnh nghia acid, baz cua Leis loai tru lun vai tro cua H
va t trng tm trn i
in tu cua lin kt phi tri.
Acid Leis la cht co th thi nhn mt i in tu cua lin kt phi tri.
Baz Leis la cht co th cung cp mt i in tu tao ra lin kt phi tri.
Vi du: H
NH
3

NH
Nh vy phan ung tao phuc cung co th xem la phan ung acid, baz voi cation trung
tm ong vai tro la acid nhn cac i in tu tu cac ligand ong vai tro baz.
Vi du: Ag
2CN
CNAgCN.
3./. Cn bng !5. n"#! B Th.ng )H
Noc la dung mi lng tinh, vua co kha nng cho proton, vua co kha nng nhn
proton.
H
2
O
OH
-
H
2
O H
H
3
O

H
2
O H
2
O
H
3
O

OH
-
acid 1 baz 2 acid 2 baz 1
tng ung voi 2 cp acid/baz lin hop: H
2
O/ OH
-
va H
3
O

/ H
2
O.
Mc du noc in ly yu nhng ngoi ta vn o oc dn in va xac nh oc
gia tr hng s cn bng theo nh lut tac dung khi long:
[ ] [ ]
[ ]
2
2
3
I J
IJ I J
K
+
3,2.10
-1
(o 2
0
C)
Vi in ly cua noc rt nho nn xem nh nng cua nc khng i va bng:
1000(g)/1,02(g/mol), mol/l.
Thay vao phng trinh trn thu oc:
[ ] [ ] [ ]
[ ] [ ] [ ]
[ ] [ ]
[ ] [ ] l %-l IJ I J
IJ I J K
IJ I J I J K
IJ I J I J K
I J
/ 10
10
02 , 1
1000
. 10 . 2 , 3
3
1
3
2
1
3
2
2
3
2
2
2
+
+
+
+

,
_

Trong o I J
K
2
la tich s ion cua noc. Tich s nay thay i theo nhit .
Tich s ion cua noc o mt s nhit
Nhi,t :C
(
0
C)
1
10
2
I J
K
I J
pK
2
)HS)KH
0 0,11 1, ,
10 0,2 1, ,2
2 1,00 1,0 ,0
0 , 13,2 ,2
100 1,30 12,2 ,1
300 00,0 11,0 ,0
Th.ng )H
+

I J
. pJ
3
lg
[ ]
+
I J pJ
3
lg
[ ]
pJ
I J
+
10
3

IJ
. pIJ lg
[ ]
IJ pIJ lg
[ ]
pIJ
IJ

10
[ ] [ ]
1
10
+
IJ J
1 + pJ pIJ
Di voi noc: pH pOH (o 2
0
C).
Trong dung dch noc nng H
3
O
thay i trong khoang 10M n 10

-1
M. Tng
ung pH cua dung dch thay i tu 1 n 1. Dua vao pH cua dung dch ngoi ta
phn chia thanh 3 loai: acid, baz va trung tinh.

3.3. Tu.n h, giU. H
.
&2 H
b
!5. 7Ct !V) .!id B b.Q ;iWn hP)
5KLng 9 cB. .c,M 6.> N hOng s= .c, #K
.
) 1< hOng s= 6.> #K
6
)
Cho A/B la cp acid/baz lin hop. Ta co phan ung:
A H
2
O
B H
3
O
Hng s cn bng cua phan ung trn oc biu din bng h thuc:
[ ] [ ]
[ ] [ ] I J "
4 I J
K
2
3
+
Tng tu nh trn
[ ]
[ ] [ ]
[ ] "
4 I J
I J K K
.

+
3
2
K
a
la hng s acid. Acid cang manh tuc la nhong proton cho noc cang nhiu thi K
a
cang lon va ngoc lai. Nn K
a
la ai long c trng cho cong acid. Di voi acid
manh thi K
a
. D n gian hoa tu y chung ta thay H
3
O

bng H
.
[ ] [ ]
[ ] "
4 J
K
.

+
D thun loi cho vic tinh toan ngoi ta con dung ai long pK
a
-lgK
a
.
Tng tu nh vy nu xet qua trinh xay ra khi hoa tan baz B trong noc:
B H
2
O
A OH
-
Va
[ ] [ ]
[ ] [ ] I J 4
" IJ
K
2
[ ]
[ ] [ ]
[ ] 4
" IJ
I J K K
6

2
[ ] [ ]
[ ] 4
" IJ
K
6

pK
b
-lgK
b
K
b
oc gi la hng s baz va c trng cho cong cua baz. Khi baz manh thi K
b

.
uan h giua K
a
va K
b
cua cp acid/baz lin hop
[ ] [ ]
[ ] "
4 J
K
.

+
[ ] [ ]
[ ] 4
" IJ
K
6

[ ] [ ]
[ ]
[ ] [ ]
[ ]
[ ] [ ]
I J 6 .
K IJ J
4
" IJ
"
4 J
K K
2
.

+
+
I J 6 .
K K K
2

1
2
+
I J 6 .
pK pK pK
(o 2
0
C)
Vi du: HCl la mt acid manh co K
a
nn baz lien hop cua no la Cl
-
co K
b
0, tuc
la mt baz v cung yu. NH
3
la mt baz yu co K
b
10
-,
, nn acid lin hop cua no la
NH
co K
a
10
-1
/10
-,
10
-,2
.
3.O. )H trong !(! h, .!idXb.Q
D tinh nng cn bng cua ion H
3
O
, tu o tinh pH cua dung dch cac h acid-baz

trong noc noi chung, ta cn:
- Vit cac phng trinh trao i proton xay ra trong dung dch (thong la pt trao i
cua acid, baz, va ca noc).
- Lp phng trinh bao toan proton trong h: S mol proton cac acid cho lun bng
s mol proton cac baz nhn.
- Pt hng s acid, hng s baz (khng cn i voi acid va baz manh).
- Pt bao toan khi long cua cac cu tu trong dung dch.
tu o lp phng trinh cho nng cn bng cua ion H
3
O
.
3.O.1. )H !5. h, .!id 7$nh, b.Q 7$nh
)H !5. h, .!id 7$nh
Cac acid manh thong gp u la cac n acid nh HCl, HNO
3
, HBr, H, HSCN,
HClO
, .) chi tru H
2
SO
la a acid (K
1
, K
2
10
-2
).
Gia su co HA voi nng la C
A
. Trong dung dch gm co 2 thanh phn la HA va
H
2
O.
- Phng trinh trao i proton:
HA
A
-
(1)
H
2
O
OH
-
(2)
- Lp phng trinh bao toan proton trong h:
H
A
-
OH
-
(3)
- Pt hng s acid:
[ ] [ ]
[ ] J"
" J
K
.
+
()
- Pt bao toan khi long cua cac cu tu trong dung dch:
C
A
A
-
HA ()
Vi HA la acid manh nn hoan toan phn li trong noc nn () C
A
A
-
. Va K
a

, pt () trong trong hop nay khng dung n.
Trong dung dch noc o 2
0
C co
H
.OH
-
10
-1
Nn
[ ]
[ ] [ ]
+

J J
K
IJ
I J
1
10
2

Thay C
A
va OH
-
vao pt (3) ta co:
[ ]
[ ]
+
+
+
J
5 J
"
1
10
Hay:
[ ] [ ] 0 10
1
2

+ +
J 5 J
"
()
D tinh H
ta chia lam hai trong hop:

a) Nng acid trong dung dch C
A
_ 10
-
M
Khi o ta co th bo qua OH
-
trong pt (3) tuc khng tinh n su phn li cua noc. Vi
mt cach gn ung thi:
[ ]
[ ]
"
5
J
IJ
100
1
10
10
1
<

+
.
Nh vy: pt () tro thanh:
[ ]
"
"
5 pJ
5 J
lg
+
b) C
A
10
-
M: dung dch rt long
Khi o
[ ]
"
5 IJ
100
1
>
nn phai tinh n su phn li cua noc.

Giai pt () la phng trinh bc 2 theo H
ta co:
[ ]
2
2
I J " "
K 5 5
J
+
+
P ,0* tinh pH dung dch HCl co C
A
10
-3
M, C
A
.10
-
M
5
"
:&Q
RF
S* Vi [ ]
"
5 IJ
100
1
10
10
10
11
3
1
<

nn co th bo qua su phn li cua noc.

[ ]
3 lg
10
3

+
"
"
5 pJ
5 J
5
"
:T.&Q
R'
S* vi dung dch qua long nn khi tinh nng H
phai tinh ca su phn li

cua noc.
Nh vy: [ ]
1
10 . 2 , 1
2
10 10 10 .
2
2

+
I J " "
K 5 5
J
pH-lgH
,.
)H !5. h, b.Q 7$nh
Cac acid manh thong gp NaOH, KOH.
Gia su co baz B co nng la C
B
. Trong dung dch gm co 2 thanh phn la B va
H
2
O.
Ta co phan ung cho nhn proton nh sau:
B H
2
O
BH
OH
-

H
2
O
OH
-

OH
-
BH

C
B
B BH

Trong dung dch noc o 2
0
C co
H
.OH
-
10
-1
Nn
[ ]
[ ] [ ]
+

IJ IJ
K
J
I J
1
10
2

[ ]
[ ]
+
IJ
5 IJ
4
1
10
Hay:
[ ] [ ] 0 10
1
2

IJ 5 IJ
4

Cung chia ra lam hai trong hop nh /v acid manh:
c) Nng baz trong dung dch C
B
_ 10
-
M
[ ]
4
4
4
5 pJ
5 pIJ
5 IJ
lg 1
lg
+

d) C
B
10
-
M: dung dch rt long
[ ]
,
_
+
+
,
_
+

+
lg 1
2
lg
2
2
2
2
I J 4 4
I J 4 4
I J 4 4
K 5 5
pJ
K 5 5
pIJ
K 5 5
IJ
3.O./. )H !5. h, :%n .!id <?u, :%n b.Q <?u
%n .!id <?uE
et dung dch mt n acid yu HA co nng ban u la C
A
va hng s acid K
a
.
Trong dung dch xay ra cac qua trinh cho nhn proton sau:
HA
A
-
,
[ ] [ ]
[ ] J"
J "
K
.
+

[ ]
[ ]
[ ]
"
J" K
J
.
H
2
O
OH
-
,
[ ] [ ]
+
IJ J K
I J
2

Pt nh lut bao toan proton:
H
A
-
OH
-
A
-
H
- OH
-
Pt bao toan khi long /v HA:

A
-
HA C
A
HA C
A
- A
-
C
A
- H
OH
-
Thay nng HA va A
-
vao ct tinh H
ta co:
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+
IJ J
IJ J 5 K
J
" .
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+
+

IJ J
IJ J 5
K J
"
.
, trong o
[ ]
[ ]
+
J
K
IJ
I J
2
Trong phn lon cac trong hop ta co th n gian hoa. Cu th:
a) Acid kha yu, K
a
kha nho, C
A
kha lon:
[ ] [ ]
+
J IJ
100
1
,
[ ]
"
5 J
+
100
1
Thi ta co th bo qua OH
-
troc H
va H
troc C
A
, khi o pt tro thanh:
[ ]
( )
[ ]
+
+

J
5
K J
"
.
hay
[ ]
" .
5 K J
+
b) Acid khng qua yu, K
a
kha lon
[ ] [ ]
+
J IJ
100
1
nhng
[ ]
"
5 J >
+
100
1
Thi ta co th bo qua OH
-
troc H
, nhng khng th bo qua H
troc C
A
, khi o
pt tro thanh:
[ ]
[ ] ( )
[ ]
[ ] [ ] 0
2
+

+ +
+
+
+
" . .
"
.
5 K J K J
J
J 5
K J
[ ]
2
2
" .
.
.
5 K K K
J
+
+
[ ]
" .
.
.
5 K
K K
J + +
+
2 2
2
c) Acid qua yu, K
a
qua nho, K
a
10
-
[ ] [ ]
"
5 J IJ
100
1

+

Ta co th bo qua H
troc C
A
nhng khng th bo qua OH
-
troc H
. Pt tro
thanh:
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ]
[ ]
1
1
2
2
10
0 10
0
+
+
+ +
+
+
+

" .
" .
" .
"
.
5 K J
5 K J
5 K IJ J J
IJ J
5
K J
Nh vy bit nn dung cng thuc nao ta cn so sanh OH
-
, H
va C
A
. D lam
oc iu o ta thuc hin cac boc sau:
- tinh gia tr gn ung cua H
khi khng tinh n su phn li cua noc:

[ ]
" . g
5 K J
+
- Tinh gia tr gn ung cua OH
-
dua vao H
g
:
[ ]
[ ]
" . g
g
5 K J
IJ
1 1
10 10
- Nu:
[ ] [ ]
g g
J IJ
+

100
1
va
[ ]
" g
5 J
+
100
1
co th bo qua OH
-
troc H
va
H
troc C
A
trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+
+

IJ J
IJ J 5
K J
"
.
va khi o
[ ] [ ]
" . g
5 K J J
+ +
- Nu
[ ] [ ]
g g
J IJ
+

100
1
va
[ ]
" g
5 J >
+
100
1
thi ta chi co th bo OH
-
troc H

trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+
+

IJ J
IJ J 5
K J
"
.
, khi o
[ ]
[ ] ( )
[ ]
[ ] [ ] 0
2
+

+ +
+
+
+
" . .
"
.
5 K J K J
J
J 5
K J
[ ]
" .
.
.
5 K
K K
J + +
+
2 2
2
- Nu K
a
rt nho va
[ ] [ ]
"
5 J IJ
100
1

+
ta chi bo qua H
troc C
A
trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+
+

IJ J
IJ J 5
K J
"
.
, khi o
[ ]
[ ] [ ]
[ ]
1
10
+
+
+
+

" .
"
.
5 K J
IJ J
5
K J
Vi du:
Y.Q <?u
et dung dch mt n baz B co nng ban u la C
B
va hng s cn bng la K
b
.
Trong dung dch xay ra cac qua trinh trao i proton nh sau:
B H
2
O
BH
OH
-

[ ] [ ]
[ ] 4
4J IJ
K
6
+

[ ]
[ ]
[ ]
+
4J
4 K
IJ
6
H
2
O
OH
-

OH
-
BH
BH
OH
-
- H

C
A
B BH
B C
A
- BH
B C
A
- OH
-
H
Thay vao cng thuc tinh OH

-
ta co:
[ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ] [ ]
+
+
J IJ
J IJ 5
K IJ
4J
4 K
IJ
4
6
6
Cung xet 3 trong hop nh i voi acid n yu va cac boc tin hanh tng tu.
a) Baz kha yu, K
b
kha nho, C
B
kha lon:
[ ] [ ]
+
IJ J
100
1
,
[ ]
4
5 IJ
100
1
Thi ta co th bo qua H
troc OH
-
va OH
-
troc C
B
, khi o pt tro thanh:
[ ]
( )
[ ]

IJ
5
K IJ
4
6
hay
[ ]
4 6
5 K IJ
b) Baz khng qua yu, K

b
kha lon
[ ] [ ]
+
IJ J
100
1
nhng
[ ]
4
5 IJ >
100
1
Thi ta co th bo qua H
troc OH
-
, nhng khng th bo qua OH
-
troc C
B
, khi
o pt tro thanh:
[ ]
[ ] ( )
[ ]
[ ] [ ] 0
2
+
4 6 6
4
6
5 K IJ K IJ
IJ
IJ 5
K IJ
[ ]
2
2
4 6 6 6
5 K K K
IJ
+
[ ]
4 6
6
6
5 K
K K
IJ + +
2 2
2
c) Baz qua yu, K
b
qua nho, K
b
10
-
[ ] [ ]
4
5 J IJ
100
1

+

Ta co th bo qua OH
-
troc C
A
nhng khng th bo qua H
troc OH
-
. Pt tro
thanh:
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ]
[ ]
1
1
2
2
-
10
0 10
0
OH

+
+
+

4 6
4 6
4 6
4
6
5 K IJ
5 K IJ
5 K IJ J IJ
J IJ
5
K
Nh vy bit nn dung cng thuc nao ta cn so sanh OH
-
, H
va C
A
. D lam
oc iu o ta thuc hin cac boc sau:
- tinh gia tr gn ung cua OH
-
khi khng tinh n su phn li cua noc:
[ ]
4 6 g
5 K IJ
- Tinh gia tr gn ung cua H
dua vao OH
-
g
:
[ ]
[ ]
4 6 g
g
5 K IJ
J
+
1 1
10 10
- Nu:
[ ] [ ]
g g
IJ J
+

100
1
va
[ ]
4 g
5 IJ
100
1
co th bo qua H
troc OH
-
va
OH
-
troc C
B
trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+

J IJ
J IJ 5
K IJ
"
.
va khi o
[ ] [ ]
4 6 g
5 K IJ IJ

- Nu
[ ] [ ]
g g
IJ J
+

100
1
va
[ ]
4 g
5 IJ >
100
1
thi ta chi co th bo H
troc OH
-

trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+

J IJ
J IJ 5
K IJ
4
6
, khi o
[ ]
[ ] ( )
[ ]
[ ] [ ] 0
2
+
4 6 6
"
6
5 K IJ K IJ
IJ
IJ 5
K IJ
[ ]
4 6
6
6
5 K
K K
IJ + +
2 2
2
- Nu K
b
rt nho va
[ ] [ ]
4
5 J IJ
100
1

+
ta chi bo qua OH
-
troc C
B
trong pt
[ ]
[ ] [ ] ( )
[ ] [ ]
+
+
+

J IJ
J IJ 5
K IJ
4
6
, khi o
[ ]
[ ] [ ]
[ ]
1
10

+

4 6
4
6
5 K IJ
J IJ
5
K IJ
Vi du:
3.O.3. Zung d!h :,7 B )H !5. dung d!h :,7
Dung dch m la dung dch co th giu pH dung dch o mt gia tr nh sn va giu
pH nay gn nh khng i trong sut qua trinh phan ung (du trong dung dch co xut
hin mt it H
, OH
-
hay co b pha long.
Dung dch m thng dung nht la hn hop cua acid yu HA va baz lin hop cua no
A
-
(doi dang mui NaA). Vi du:
Dm n la hn hop cua 1 cp acid/baz lin hop
- Dm axtat: CH
3
COOH / CH
3
COONa
- Dm cacbonat: NaHCO
3
/ Na
2
CO
3
- Dm Amoni: NH
Cl / NH
OH
Dm kep la hn hop cua nhiu cp acid/baz lin hop.
- Dm pht phat: Na
2
HPO
/ Na
3
PO
(hoc NaH
2
PO
/ Na
2
HPO
; H
3
PO /
NaH
2
PO
).
)H !5. dung d!h :,7
et dung dch co chua acid HA voi nng ban u la C
A
va baz lin hop o dang
mui NaA voi nng C
B
. Trong dung dch tn tai cac sau:
NaA Na
A
-
HA
A
-

[ ] [ ]
[ ] J"
J "
K
.
+

[ ]
[ ]
[ ]
"
J" K
J
.
H
2
O
OH
-
Pt trung hoa in tich:
A
-
OH
-
H
Na
A
-
OH
-
H
C
B
A
-
H
C
B
- OH
-
A
-
C
B
(H
- OH
-
)
Pt bao toan khi long cua HA va A
-
:
A
-
HA C
B
C
A
HA C
B
C
A
- A
-
HA C
B
C
A
- H
- C
B
OH
-
HA C
A
(H
- OH
-
)
Thay vao pt tinh H
:
[ ]
[ ]
[ ]
[ ]
[ ] [ ] ( )
[ ] [ ] ( )
+
+
+
+
+

IJ J 5
IJ J 5
K J
"
J" K
J
4
"
.
.
Tuy theo mi trong co tinh acid hay baz ta co th n gian hoa cng thuc.
Nu dung dch co tinh acid (acid kha manh, baz lin hop kha yu, pK
a
nho), H
~~
OH
-
, co th bo qua OH
-
:
[ ]
[ ] [ ] ( )
[ ] [ ] ( )
[ ]
[ ]
[ ]
+
+
+
+
+
+
+

+

J 5
J 5
K J
IJ J 5
IJ J 5
K J
4
"
.
4
"
.
Nu dung dch co tinh baz (acid kha yu, baz lin hop kha manh, pK
a
lon), H

OH
-
, co th bo qua H
:
[ ]
[ ] [ ] ( )
[ ] [ ] ( )
[ ]
[ ]
[ ]
+
+
+
+
+

+

IJ 5
IJ 5
K J
IJ J 5
IJ J 5
K J
4
"
.
4
"
.
Trong hop hay gp nht la C
A
va C
B
u lon hn nhiu so voi H
, OH
-
, khi o:
[ ]
[ ] [ ] ( )
[ ] [ ] ( )
[ ]
4
"
.
4
"
.
4
"
.
5
5
pK pJ
5
5
K J
IJ J 5
IJ J 5
K J
lg

+

+
+
+
+
Vi du:
5U ch gV pJ gWn nhK khng cB. ,ung ,@ch !%
NaA Na
A
-
(1)
HA
A
-
(2)
Vi NaA la cht in ly manh, phn li hoan toan trong noc nn A
-
tao thanh tu pt (1)
s lam cho cn bng pu (2) dch chuyn v phia trai. Trong dung dch o trang thai cn
bng tn tai HA doi dang phn tu (gn nh khng phn li), va A
-
. Chinh 2 thanh phn
nay giu cho pH khng i (thay i rt it).
- T/h 1. Nu ta thm mt it H
(H
nho hn so voi C
A
, C
B
) thi phn lon H
s tham
gia vao pu voi A
-
:
A
-
H
HA
Khi o:
HA C
A
H
A
-
C
B
- H
Gia tr pH cua dung dch luc o s la :

[ ]
[ ]
+
+
+

J 5
J 5
pK pJ
4
"
.
lg
2
So voi troc khi thm acid:
4
"
.
5
5
pK pJ lg
1

Vi ham lg bin thin rt chm nn pH thay i khng ang k.
Tng tu khi thm mt long nho OH
-
hay thm noc vao dung dch cua khng lam
thay i nhiu gia tr pH.
?!% n$ng
D so sanh cht long (kha nng giu pH c nh) cua nhung dung dch m khac
nhau ngoi ta dung mt ai long gi la m nng.
Dm nng cua dung dch m la ai long o kha nng cua dung dch m chng lai
mi thay i pH khi thm vao dung dch mt it acid hay baz.
Dm nng oc nh nghia bng s mol cua mt baz manh (hoc mt acid manh)
cn thm vao 1 lit dung dch m pH cua no tng ln (hoc giam i) 1 n v.
Gi pH la bin thin cua pH gy ra khi thm mt long C
A
cua acid manh
hoc C
B
cua baz manh. Khi o m nng oc xac nh boi ai long .
pJ
5
pJ
5
" 4

Dm nng co gia tr cuc ai khi nng baz va acid lin hop bng nhau.
3.O.O. )H !5. dung d!h :. .!id, :. b.Q
Di voi a acid yu va a baz yu, hng s acid va baz tng ung voi cac bc khac
bit nhau rt lon. Thong thi hng s acid (baz) cua bc tip theo nho hn bc troc o
10
ln. Do o khi tinh pH cua dung dch ta coi nh a acid (baz) la acid (baz) n yu.
Va tinh pH nh xet o trn.
H
3
PO
3
H
H
2
PO
3
-
K
a1
,.10
-3
H
2
PO
3
-
H
HPO
3
2-
K
a2
,2.10
-
HPO
3
2-
H
PO
3
3-
K
a2
,2.10
-13
Xng 9 c+c -n Y %9t pJ Z+c @nh
Vi du, xet a acid H
2
A. (V trn PP)
Khi pH pK
a1
: H
2
A lon nht
pH pK
a1
: H
2
A HA
-
pK
a1
pH pK
a2
: HA
-
lon nht
pH pK
a2
: HA
-
A
2-
pH ~ pK
a2
: A
2-
lon nht.
Tng tu i voi baz a chuc.
3.O.[. )H !5. dung d!h !h9t ;"\ng t*nh
a) pH dung dch mui co anion lng tinh:
et mui NaHA phn li trong noc tao anion HA
-
co tinh cht lng tinh.
HA
-
H
2
O
A
2-
H
3
O
K
HA
a
HA
-
H
2
O
H
2
A OH
-
K
HA
b
Nu K
HA
a
~ K
HA
b
thi dung dch co tinh acid
K
HA
a
K
HA
b
thi dung dch co tinh baz.
Vi du:
Tinh pH
et dung dch mui NaHA co nng ban u la C. Hng s acid cua H
2
A tng
ung voi 2 bc la K
a1
va K
a2
.
[ ][ ]
[ ] " J
J J"
K
.
2
1
+
[ ][ ]
[ ]
J"
J "
K
.
2
2
[ ]
2 1 . .
K K J
+
) (
2
1
2 1 . .
pK pK pJ +
b) Dung dch chua acid va baz khng lin hop
Nu C
A
C
B
thi
[ ]
2 1 . .
K K J
+
) (
2
1
2 1 . .
pK pK pJ +
Nu C
A
mC
B
[ ]
[ ] [ ]
+ +
+
+
+ J K
%K
J K
J
.
.
. 1
1
2
3.O.]. )H !5. dung d!h 7uGi
a) Mui cua acid manh va baz manh: NaCl, KNO
3
, ...
Cac mui nay trong noc b phn li hoan toan thanh cation va anion. Cac ion khng
b thuy phn (khng ion hoa oc noc) nn pH (pH cua noc nguyn cht).
b) Mui cua acid manh va baz yu: NH
Cl gm cation NH
co tinh acid yu va Cl
-
co tinh baz v cung yu. Nn co th tinh pH dung dch mui nh trong hop acid yu
thng thong.
NH
Cl
NH
Cl
-
NH
H
2
O
NH
3
H
3
O

c) Mui cua acid yu va baz manh: CH
3
COONa gm cation Na
co tinh acid v cung

yu va anion CH
3
COO
-
co tinh baz yu. Nn tinh pH nh i voi dung dch baz yu
thng thong.
CH
3
COONa
Na
CH
3
COO
-
CH
3
COO
-
H
2
O
CH
3
COOH OH
-
d) Mui cua a acid yu
et dung dch NaA
2
co hng s acid cua H
2
A la K
a1
va K
a2
.
Na
2
A 2Na
A
2-
Co th xem A
2-
la mt a baz ln lot nhn proton cua noc theo 2 nc:
A
2-
H
2
O
HA
-
OH
-
(K
b2
)
HA
-
H
2
O
H
2
A OH
-
(K
b1
)
Vi K
a1
~~ K
a2
, hay K
b1
K
b2
va A
2-
~~ HA
-
, nn xem nh dung dch chi chua
baz yu A
2-
va tinh pH dua vao K
b2
.
3.O.]. )H !5. h^n hP) .!id hoV! h^n hP) b.Q
Hn hop acid
a) Hai acid manh: tinh ging nh acid manh thng thong.
b) Mt acid manh va mt acid yu: xet hn hop 2 acid HCl co nng C
A1
va
CH
3
COOH co nng C
A2
va K
a
HCl H

Cl
-
CH
3
COOH
H

CH
3
COO
-

-) Nu C
A1
~ C
A2
co th bo qua su ion hoa cua CH
3
COOH. pH tinh nh trong
trong hop chi co HCl.
-) Nu C
A1
C
A2
phai tinh ca su ion hoa cua acid yu.
Pt bao toan proton (bo qua su phn li cua noc):
H
Cl
-
CH
3
COO
-
C
A1
CH
3
COO
-
Pt bao toan khi long cua CH

3
COOH:
C
A2
CH
3
COO
-
CH
3
COOH
Vi CH
3
COOH la acid yu nn s phn tu phn li rt nho so voi khng phn li.
C
A2
CH
3
COOH
[ ] [ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ]
2
0
2
2
1 1
2 1
2
1
2
3
3
3
3
" . " "
" . "
"
"
.
.
.
5 K 5 5
J
5 K J 5 J
5 J
5
K J
5II 5J
5IIJ 5J K
J
5IIJ 5J
5II 5J J
K
+ +
+
+ +
+
+
+
+
c) Hn hop hai acid yu
[ ]
[ ]
2 2 1 1
2 2 1 1
2
" . " .
" . " .
5 K 5 K J
5 K 5 K J
+
+
+
+
Tng tu i voi hn hop baz
a) Hn hop 2 baz manh
b) Mt baz manh co nng C
B1
va mt baz yu co nng C
B2
va K
b
-) Nu C
B1
~ C
B2
co th bo qua su ion hoa cua baz yu. pH tinh nh trong trong
hop chi co acid manh.
-) Nu C
B1
C
B2
phai tinh ca su ion hoa cua baz yu:
[ ]
2
2
2
1 1 4 6 4 4
5 K 5 5
IJ
+ +
c) Hn hop hai BA yu
[ ]
2 2 1 1 4 6 4 6
5 K 5 K IJ +
Vi du
O. Cn bng !5. )h8n 3ng t$o )h3!
O.1. nh nghR. &' hP) !h9t )h3!
Tu giao trinh hoa v c chung ta bit khi cac nguyn t ring bit kt hop voi nhau
thi tao thanh cac hop cht n gian, hay con gi la hop cht bc nht, vi du Na
2
O, CuO,
., cac halogenua NaCl, CuCl
2
, . Nhung hop cht n gian lai co th kt hop voi nhau
tao thanh hp ch[t 6\c c.-, hay hp ch[t phn t/, vi du K
2
Hg
2
(Hg
2
.2K); Ag(NH
3
)
2
Cl
(AgCl.2NH
3
), K
3
Fe(CN)
(Fe(CN)
3
.3KCN), (NH
)
2
SO
.FeSO
.H
2
O. Trong nhom hop
cht phn tu oc chia lam nhiu loai nh hop cht phuc, hop cht mui kep
(NH
)
2
SO
.FeSO
.H
2
O (trong noc phn li hoan toan thanh cation),.
(NH
)
2
SO
.FeSO
.H
2
O NH
2SO
2-
Fe
2
H
2
O
Jp ch[t ph]c l< g^
Phuc cht la mt t hop gm mt hoc nhiu ion trung tm (thong la ion kim loai)
lin kt voi mt s phn tu hoc ion khac (phi tu hay ligand).
Theo nh nghia cua K.B. aximirxki : phuc cht la nhung hop cht tao oc cac
nhom ring bit tu cac nguyn tu, ion hoc phn tu voi nhung c trng : a) co su co mt
phi tri, b) khng phn li hoan toan trong dung dch (hoc chn khng) nhng long san
phm cua su phn ly cua phuc cht u co th hoa hop voi nhung cht khac, c) co thanh
phn phuc tap (s phi tri va s hoa tr khng trung nhau).
HgCl
2
HgCl
Cl
-
HgCl
Hg
2
Cl
-
Long Hg
2
u lon khi trong dung dch co ion S
2-
s tao ra kt tua HgS.
Hg
2
S
2-
HgS
Dc im thu 2 chinh la su khac bit giua phuc cht va mui kep cung nm trong
nhom hop cht bc cao.
Vi du: Ag(NH
3
)
2
, Cu(NH
3
)
2
, FeF
3-
5[u t8- ph]c ch[t
Hop cht phuc oc cu tao tu 2 phn la cu ni phi tri (cu ni) gm ion trung
tm va phi tu (ligand) lin kt truc tip voi ion trung tm va cu ngoai gm cac thanh
phn con lai cua phuc cht (co th co hoc khng). Di voi mt s phuc cht (phuc trung
hoa) khng chua thanh phn cu ngoai. Nhung thanh phn trong cu ni oc vit trong
du ngoc vung , phn cn cu ngoai bn ngoai ngoc vung. Cu ngoai la cac cation
thi vit phia troc cu ni, nu la ion m thi vit phia sau cu ni.
Vi du: LiAlH
gm cu ni la AlH
co ion trung tm Al va phi tu (ligand) H,

cu ngoai la cation Li.
K
2
Be(CO
3
)
2
Co(NH
3
)
3
Cl
3
Pt(NH
3
)
2
Cl
2
, Co(NH
3
)
3
Cl
3
khng chua cu ngoai.
_-n #h8t) trung t%* la cation ma phn tu hoc ion khac lin kt voi no tao phn
tu phuc. on trung tm thong la cac cation kim loai hoc la cac oxocation dang O
2
2
,
TiO
2
.
Co 3 loai:
- Kim loai ma ion lop ngoai cung cua no co cu hinh ging khi tr (2 hoc e). Do la
cac kim loai kim, kim th va nhm. Cac ion kim loai kim va kim th (ngoai mt s
nguyn t o 2 chu ki u) tao phuc kem bn so voi phuc cac nguyn t khac. Al
3
va cac
kim loai nhom nay tao phuc bn voi cac ion bn nh F
-
, O
2-
, trai lai tao phuc khng bn
voi cac ion to nh
-
, NH
3
, CN
-
, ..., lin kt trong cac phuc nay mang nhiu tinh ion.
- Kim loai ma ion co chua 1e o lop ngoai cung: am my in tu cua ion nay d b
bin dang nn lin kt giua ion trung tm va cac phi tu mang nhiu tinh cng hoa tr, do
o ban kinh cac phi tu cang lon, m in cua phi tu cang nho, phuc cang bn. Vi du
bn phuc giam theo thu tu O ~ N ~ F.
- on nguyn t chuyn tip: loai nay co phn lop d cha bo hoa nn co th tham
gia vao cac lin kt hoa hc tao nhiu phuc voi nhiu ligand khac nhau trong o co nhiu
phuc cht rt bn.
`h= t/ #Gg.n,)* phn tu hoc anion lin kt truc tip voi hat trung tm. Cac
liagnad thong la cac phn tu hoc ion v c, huu c.
Cac ligand co th la cac anion hoc la cac phn tu khng mang in. Cac ligand nay
co nhung i e tu do co th tao lin kt phi tri voi ion kim loai do o co th xem ligand
la baz Leis con ion kim loai la acid Leis.
Tuy theo ligand oc lin kt voi ion trung tm bng mt hay nhiu cu ni, ta co
th chia ligand ra lam 2 loai:
- ligand n nha (mt cu ni)
- ligand a nha (ni voi ion trung tm bng nhiu u ni, co th la 2, , ,. Vi du
nh diamin co 2 u ni, DTA co u ni.
a= ph= tr* S cac nguyn tu hoc nhom cac nguyn tu (s phi tu) lin kt truc tip
voi ion trung tm oc gi la s phi tri (s.p.t)cua ion trung tm o.
S phi tri thong lon hn s hoa tr.
S phi tri co th khac nhau, nhng thong gp la 2, va ung voi cac cu hinh hc
co i xung cao nht cua phuc cht la bat din (), tu din hoc vung () va thng (2).
S phi tri cua mt s ion trung tm la c nh khng phu thuc vao phi tu: Pt(V),
r(V), Cr(), Co(),...u co s.p.t. ; Pd(), Pt(), Au(), ... co s.p.t..
Mt s ion trung tm co s phi tri khac nhau phu thuc vao ban cht cua phi tu:
Cu() co s.p.t. 3, , , Ag() co s.p.t.2, 3. ...
Ngoai ra s.p.t con phu thuc vao nhit , khi tng nhit thi s.p.t. giam.
7ung lKng ph= tr cB. ph= t/*
Dung long phi tri cua mt phi tu (d.l.p.t.) la s v tri phi tri ma no chim oc
trong cu ni.
Cac phi tu lin kt truc tip voi cac ion trung tm bng mt lin kt thi co d.l.p.t.
1. Vi du nh cac gc acid hoa tr 1, cac phn tu trung hoa nh NH
3
, C
2
H
OH, H
2
O,
CH
3
NH
2
, cac ion a hoa tr nh O
2-
, N
3-
, ...
Nu mt phi tu lin kt voi ion trung tm qua hai hay mt s lin kt thi phi tu o
chim hai hay nhiu hn v tri phi tri va oc gi la phi tu phi tri hai, phi tri 3 hoc
a phi tri (hoc con gi la phi tu hai cang, ba cang hoc a cang). Cac gc acid SO
2-
,
C
2
O
2-
..., cac phn tu trung hoa nh etilendiamin (n) NH
2
-CH
2
-CH
2
-NH
2
co d.l.p.t. 2,
triaminopropan CH
2
NH
2
-CHNH
2
- CH
2
NH
2
co d.l.p.t. 3, ...
Phn tu cua cac phi tu a phi tri lin kt voi ion trung tm trong cu ni qua mt
s nguyn tu, tao thanh vong va nhung phuc cht chua phi tu tao vong oc gi la phuc
cht vong (phuc cht vong cang, cang cua, chelat). Vi du:

Su co mt cua cac nhom tao vong trong cac phuc cht chelat lam tng manh bn
so voi cac phuc cht co thanh phn tng tu nhng khng chua nhom tao vong. Su tng
bn nay gi la hiu ung chelat.
Z.nh )h()
Khi gi tn phuc cht thi troc ht gi tn cac ligand ln lot theo thu tu gc acid,
phn tu ri sau cung la moi n tn cua cac ion trung tm km mt s La M cho bit s
oxi hoa cua ion trung tm. Nu ion phuc la anion thi thm vao tn kim loai vn .t.
Nu ligand la oxyacid thi thm - vao tn cua gc acid, vi du SO
2-
(sunIato), NO
3
-
(nitrato).
Nu ligand la ion halogenua thi thm - vao tn cua halogen, vi du Cl
-
(cloro)...
Mt s anion co tn khac co tn ring nh NO
2
-
(nitro), OH
-
(hydroxo), O
2
-
(oxo),
S
2-
(sunIo), S
2
2-
(pensunIo).
Nu ligand la phn tu thi gi nh sau: H
2
O (aquo), NH
3
(ammin).
Vi du:
Co(NH
3
)
Cl
2
diclorotetraammincobalt ()
Co(NH
3
)
2
- hexaammincobalt ()
Co(C
2
O
)
3
2-
- trioxalate cobaltat ().
Ag(NH
3
)
2
Cl diammin bac () clorua
K
2
Co(NO
2
)
kali hexanitrocobaltnat ().

Nu mt nhom lin kt voi hai nguyn tu kim loai (nhom cu), thi gi tn no sau tn
tt ca cac phi tu, troc tn gi no chu , nhom cu OH
-
oc gi la -l hoc h,r-Z-.
Cac ng phn hinh hc oc ki hiu bng chu u csR hoc tr.nsR.
Phn ;o$i )h3! !h9t
.) ZA. &2o ;o$i hP) !h9t ng"_i t. )hn bi,tE
Acid phuc: H
2
SiF
, HAuCl
, H
2
PtCl
.
Baz phuc: Ag(NH
3
)
2
OH, Con
3
(OH)
3
.
Mui phuc: Ag(NH
3
)
2
Cl, K
2
Co(NO
2
)
b) Dua vao du in tich cua ion phuc (cu ni)

- Phuc trung hoa: Pt(NH
3
)
2
Cl
2
, Co(NH
3
)
3
Cl
3
- Phuc cation: LiAlH
, K
2
Be(CO
3
)
2
- Phuc anion: Co(NH

3
)
3
Cl
3
c) Dua vao ban cht cua phi tu:
- phuc aquo (hidrat) co phi tu la phn tu noc Al(H
2
O)
3
, Co(H
2
O)
(NO
3
)
2
- phuc amoniacat (amminat) co phi tu la NH
3
: Ag(NH
3
)
2
, Co(NH
3
)
Cl
3
.
- phuc hidroxo co phi tu la nhom OH
-
: K
3
Al(OH)
.
- phuc hidrua co phi tu la ion hidrua: LiAlH
.
- phuc cht c kim co phi tu la cac gc huu c: Nan(C
2
H
)
3
, Li
3
n(C
)
3
.
- phuc cht co phi tu la cac phn tu cha bo hoa nh etilen, propilen, butilen,
stiren.
d) Dua vao cu truc cua cu ni phuc:
- Theo s long ion trung tm (s nhn tao phuc): Nhung phuc cht chi co 1 ion
trung tm nh Ag(NH
3
)
2
, Cu(NH
3
)
2
, FeF
3-
gi la ph]c Un nhn. Nhung phuc co
nhiu ion trung tm cung loai, nh Fe
2
(OH)
2
, Cu
3
(OH)
2
, hoc
(CN)
Co(CN)Fe(CN)
-
oc gi la ph]c ch[t . nhn.
- Dua theo su co hay khng co vong trong thanh phn cua phuc cht ngoi ta phn
bit phuc cht n gian (phi tu chi chim mt ch phi tri) va phuc cht vong.
Phn tu cua cac phi tu a phi tri lin kt voi ion trung tm trong cu ni qua mt
s nguyn tu, tao thanh vong va nhung phuc cht chua phi tu tao vong oc gi la ph]c
ch[t 1bng #ph]c ch[t 1bng c<ngM c<ng cu.M chel.t).
Jp ch[t n9 ph]c la dang cua hop cht vong chelat trong o cung mt phi tu lin
kt voi cht tao phuc bng lin kt cp e va lin kt cho nhn, vi du natri
trioxalatoIerrat (), bis n ng ().
Cu
NH
2
NH
2
O
O C O
C O
CH
2
CH
2
e) Dua vao thanh phn cua phi tu:
- Phuc cua ion trung tm la cation kim loai va phi tu la cac phn tu cht v c:
phuc hidrat (phi tu la phn tu noc) Al(H
2
O)
3
, phuc amoniacat (phi tu la NH
3
)
Ag(NH
3
)
2
.
- Phuc cua ion trung tm la cation kim loai va phi tu la cac anion v c nh Cl
-
, F
-
,
Br
-
,

NO
2
-
. Vi du Cu
3
(OH)
2
, FeF
3
.
- Phuc cua ion trung tm la cation kim loai va phi tu la cac anion hoc phn tu cht
huu c. Vi du, Fe(C
2
O
)
3
3-
, DTA (tylen Diamin Tetra Axetic axit)
Doc vit tt la H. Vi DTA tng i kho tan trong noc nn trong thuc t
ngoi ta thong dung mui inatri cua no tan nhiu trong noc. Mui o Na2H2
oc gi la complexon hay Trilon B.
Cac complexon tao oc phuc bn voi hang chuc ion kim loai. Cac phuc nay
thoa mn cac iu kin cua nhung phan ung dung trong phn tich th tich, vi vy
ngay nay ngoi ta su dung rt rng ri phng phap chun tao phuc dung cac
complexon oc gi la phng phap chun complexon.
Nhung phuc cht co nhiu phi tu khac nhau oc gi la phuc d phi. Vi du,
Pt(NH
3
)
2
Cl
2
, (NH
3
)
CoNH
2
Co(NH
3
)
.
O./. Hng @G b'n &2 6h`ng b'n !5. )h3! !h9t
et phuc ML phn li theo phan ung (khng ghi in tich):
ML
M L
Hng s cn bng cua phan ung:
[ ] [ ]
[ ] SG
G S
K

Hng s K gi la hng s khng bn (hng s phn li) cua phuc cht. Phuc cang bn
thi hng s khng bn K cang nho.
Ngoai ra ta con dung hng s ao ngoc cua hng s khng bn gi la hng s bn
(hng s tao thanh) . Phuc cang bn thi hng s bn cang lon.
[ ]
[ ] [ ] G S
SG
K

1
Giua M va L co th co nhiu phuc ML

n
, ML
n-1
, ML
n-2
, ., ML. Mi phuc cht ln
lot phn li cho ra phuc cht k tip.
ML
n

ML
n-1
L
[ ] [ ]
[ ]
n
n
SG
G SG
K

1
1
ML
n-1
ML
n-2
L
[ ] [ ]
[ ]
1
2
2
n
n
SG
G SG
K
ML
M L
[ ] [ ]
[ ] SG
G S
K
n

Cac hng s K
1
, K
2
, ... K
n
oc gi la hng s khng bn lin tip, khi o co:
K
1
~ K
2
~ ... ~ K
n-1
~ K
n
Hng s khng bn tng hop (tng cng) cua phuc cht:
KK
1
. K
2
.... K
n

Hng s bn tng hop (tng cng) cua phuc cht:

1
.
2
....
n

O.3. NNng :C !n bng !5. !(! !9u ta trong dung d!h B TH
Di voi h phuc tao boi ion trung tm M va phi tu L phuc ch ML
n
co s phi tri
cuc ai la n va cac hng s bn tung nc ln lot la
1
,
2
, .,
n
.
M L ML
1
ML L ML
2

2
............................................
ML
n-1
L ML
n

n
Nng cac cu tu trong dung dch tinh theo cng thuc sau:
n
n
S
G G G
5
S
... ... 1

2 1
2
2 1 1
+ + + +
S
G
5
S
1

1
, 1
+
n
n
S
G G G
G 5
SG
... ... 1

2 1
2
2 1 1
1

+ + + +
S
G
G 5
SG
1

1
, 1
1
G
G 5
SG
1

1
, 1
, 1
O.O. C(! <?u tG 8nh h"bng :?n :C b'n !5. )h3! !h9t
.) )H dung d!h
et trong hop n gian ML.
ML
M L
[ ] [ ]
[ ] SG
G S
K

on H
va OH
-
co th anh hong n cn bng trn, tuc la anh hong n bn
cua phuc cht do hai phan ung phu sau:
- Phan ung kt hop giua H
va ligand L (vi L la mt baz). Phan ung tao ra HL, H

2
L,
. H
p
L. Dung dch cang acid, phan ung phu giua H
va ligand L xay ra cang manh, phuc

cht cang d b phn li. Nh vy nu chi k n phan ung H
va ligand L thi bn cua

phuc cht cang giam khi acid tng (pH giam) va phuc cang bn khi pH tng.
- Phan ung kt hop giua M va OH
-
. Cation la mt acid co khuyng hong kt hop voi
OH
-
cho ra MOH, M(OH)
2
,. M(OH)
p
. Dung dch cang chua nhiu OH
-
, phan ung giua
M va OH
-
manh thi bn cua phuc cht giam khi pH tng.
Tu hai phan ung trn ta thy iu trai ngoc nhau.
Thuc ra voi phn lon cac cation (tru cac cation qua acid) va cac ligand co tinh baz v
cung yu) thi o pH khng qua lon (co th lon hn mt ti) phan ung giua H
va ligand L
quan trng hn phan ung giua M va OH
-
(vi phuc H
p
L bn hn M(OH)
p
). Tuc la o pH
khng qua lon khi tng pH thi bn cua phuc cht tng. Tuy nhin khi pH kha lon thi
khi o phan ung phu giua M va OH
-
chim u th va bn cua phuc cht s giam khi
pH tng.
Kt lun: khi tng dn pH tu nhung gia tr thp thi bn cua phuc cht tng, qua
mt cuc ai va sau o giam dn nu ta tip tuc tng pH.
b) anh hong cua cac cht tao phan ung khac:
Trong dung dch co th co cac ligand khac tao phuc voi cation cua phuc hoc cac ion
kim loai khac co th tao phuc voi ligand cua phuc.
Vi du: gia su ngoai n
2
va
-
tao phuc n
2-
trong dung dch co NH
3
tao phuc voi
n
2
. Ngoai ra phan ung phu giua
-
voi H
va n
2
voi OH
-
, ta con co thm mt phan
ung phu o la n
2
va NH
3
.
Hng s bn iu kin.
Gia su ion kim loai M
n
, ngoai vic tham gia phan ung tao phuc chinh voi anion
DTA
-
:
con tham gia phan ung phu voi phi tu L tao nn cac phuc ML, ML
2
. ML
m
va
anion
-
con tham gia phan ung voi cac ion H
tao thanh H
3-
, H
2
2-
, H
3
-
, H
.
Trong iu kin nay hng s bn iu kin
M
cua phuc M
n-
oc nh nghia nh sau:
Trong o: M` la tng nng cn bng cac dang tn tai cua M
n
, tru phuc M
n-
,
tuc la:
,
la tng cac nng cn bng cua cac dang tn tai cua
-
, tru phuc M
n-
,
tuc la:
Nu ky hiu hng s bn tung nc cua cac phuc ML, ML
2
., ML
m
ln lot la
1
,
2
,
.
m
va cac hng s axit tung nc cua H
ln lot la K
1
, K
2
, K
3
, K
. thi ta co:
Va
Tu o suy ra:
Do hng s bn iu kin chi la hng s trong nhung iu kin xac nh. Tai nhung
iu kin xac nh, gia tr hng s bn iu kin cua mt phuc cang lon thi phuc o cang
bn tuc la trong iu kin o phuc tao thanh cang hoan toan. Hng s khng bn iu
kin K
M
la nghch ao cua hng s bn iu kin.
O.[. Hng @G b'n &2 6h`ng b'n :i'u 6i,n X TH
O.]. cng d4ng )h8n 3ng t$o )h3! trong h-. )hn t*!h X TH
[. Cn bng !5. )h8n 3ng t$o th2nh hP) !h9t *t t.n
[.1. i'u 6i,n t$o th2nh 6?t t5.. Tui ;uIt t*!h @G t.n
Phan ung kt tua la phan ung hoa hc xay ra khi mt trong cac san phm tao thanh
la cht rn it tan. Cht rn it tan oc gi la cht kt tua.
Tch s= t.n #T)
Khi thm dung dch NaCl vao dung dch AgNO
3
, s co cn bng sau:
NaCl AgNO
3
Na NO
3
AgCl
Cl
-
Ag
AgCl
ua trinh dung lai khi co su cn bng giua qua trinh hoa tan va qua trinh kt tua, tuc
la tc kt tua bng tc hoa tan.
Tc cua qua trinh kt tua v
kt
ti l thun voi din tich b mt cua kt tua tip xuc
voi dung dch va hoat cac ion tao thanh kt tua:
a . . k 1
5l "g
kt

+
1

Tc hoa tan kt tua ti l voi din tich b mt s cua kt tua tip xuc voi dung dch:
a k 1
ht

2
Khi at trang thai cn bng: v
kt
v
ht
a k a . . k
5l "g

+
2 1
Trong o k
1
, k
2
la cac hng @G tG! :C. Tu o suy ra:
"g5l
5l "g
T
k
k
. .
+
2
1
Nh vy trong dung dch bo hoa cua AgCl, o mt nhit xac nh, tich s hoat
cua cac ion Cl
-
va Ag
la mt hng s gi la tich s tan cua AgCl va ki hiu bng T

AgCl
.
+

5l "g
"g5l
. . T
Trong trong hop tng quat, i voi cht it tan co cng thuc la A
m
B
n
thi tich s tan
cua no la:
A
m
B
n

mA nB
n
4
%
" 4 "
. . T
n %

Nu A
m
B
n
la cht kho tan (tuc nng cua cac ion trong dung dch bo hoa rt nho)
va trong dung dch khng con ion nao khac thi luc ion cua dung dch kha nho va ta co th
coi hoat cua cac ion bng nng cua chung, do o tich s tan s bng:
[ ] [ ]
n %
4 "
4 " T
n %

H thuc nay la ni dung cua tich s tan. Theo ni dung cua quy lut nay thi:
a) Khi
[ ] [ ]
n %
4 "
n %
T 4 " <
tuc la tc hoa tan lon hn tc kt tua, khi o B va A
khng kt hop voi nhau tao thanh kt tua. Dung dch o iu kin nay gi la dung dch
cha bo hoa. Nu ta cho thm cht rn A
m
B
n
vao dung dch thi cht rn s tan thm cho
n khi
n
4
%
" 4 "
. . T
n %

.
b) Khi
[ ] [ ]
n %
4 "
n %
T 4 "
, luc nay tc qua trinh hoa tan bng tc qua trinh kt
tua. Kt tua khng tao thm ma cung khng hoa tan thm. Dung dch o trang thai nay gi
la dung dch bo hoa vi nu thm A
m
B
n
vao dung dch thi no cung khng tan thm nua.
c) Khi
[ ] [ ]
n %
4 "
n %
T 4 " >
tuc tc kt tua lon hn tc hoa tan, cac ion A va B s
hoa hop voi nhau tao thanh kt tua A
m
B
n
lam giam hoat cua chung cho n khi
[ ] [ ]
n %
4 "
n %
T 4 "
. Dung dch o trang thai nay gi la dung dch qua bo hoa.
[./. dGi ;iWn h, giU. :C t.n &2 t*!h @G t.n
D tan S cua mt cht A
m
B
n
la nng cua cht o trong dung dch bo hoa. D tan
thong oc biu din bng n v mg/100g, hoc mol/l.
Nh vy tan cung nh tich s tan la nhung ai long c trung cho dung dch bo
hoa. Chung co lin h voi nhau, co th tinh ai long nay khi bit ai long kia va ngoc
lai.
Trong dung dch bo hoa voi tan S cua A
m
B
n,
ta co:
a n .
a % .
%
n
4
"

+
Vi
( ) ( ) T a n % a n a %
n % n % n %

+
Nn:
n %
n %
n %
T
a
+
Do chinh la mi lin h giua tan va tich s tan.

[.3. C(! <?u tG 8nh h"bng t#i :C t.n B TH
cnh hKYng cB. -n chung
on chung la ion co trong thanh phn cua kt tua. Nu thm ion chung vao dung dch
bo hoa, tich s nng ion s tng ln, dung dch tro nn qua bo hoa va s xut hin
kt tua, tuc la tan giam i.
cnh hKYng cB. l3c -n* Khi trong dung dch chua cac ion du khng phai la ion
chung cung anh hong n tan. Vi khi o luc ion tng.
D tan tng theo luc ion cua dung dch.
cnh hKYng cB. -n J
d
#pJ) 1< ch[t t8- ph]c n 9 t.n cB. kt tB.M tch s= t.n eu
k!n
D tan cua kt tua s tng ln nu cac ion kt tua co tham gia phan ung phu voi cac
cht la co mt trong dung dch. D phan anh oc cac anh hong cua cac phan ung phu,
ngoi ta dung tich s tan iu kin.
Chng han kt tua A
m
B
n
trong dung dch co ion H
co kha nng phan ung voi B va

co cht tao phuc L co kha nng tao phuc voi A, trong dung dch co cac ion bng:
cnh hKYng cB. ch[t t8- ph]c ph0
Cac cht tao phuc phu co mt trong dung dch co th lam han ch hoc ngn can qua
trinh kt tua do su tao phuc voi kim loai: Tinh cht nay oc dung che cac ion can tro.
cnh hKYng cB. nh!t 9
Vi qua trinh hoa tan thu hoc toa nhit, no anh hong khng co qui lut nn khng
co nhung biu thuc nh long chung. Su thay i tan mt cht theo nhit co lin
quan toi hiu ung nhit khi hoa tan. Di voi nhung cht thu nhit khi hoa tan thi tan s
tng theo nhit , thi du Pb
2
tan nhiu khi un nong. D tan cua AgCl o 100
0
C lon gp
2 ln tan cua no o 10
0
C. Di voi nhung cht toa nhit thi ngoc lai, tan giam khi
nhit tng. Thi du CaSO
.0,H
2
O o 0
0
C co tan lon gp 3 ln tan cua no o
100
0
C.
cnh hKYng cB. kch thKfc h8t kt tB.
Di voi cung mt long cht kt tua co dang hat nho tan nhiu hn kt tua co dang
hat lon vi b mt cua cac tinh th nho co cac goc, canh, cac ion o v tri goc, canh d tan
hn nhung v tri khac vi cac ion o v tri bn trong b giu cht hn. Ngoai cac yu t k
trn, con co yu t khac nh qua trinh sp xp tinh th tu dang nay sang dang khac bn
hn.
[.O. cng d4ng )h8n 3ng 6?t t5. trong h-. )hn t*!h B TH
]. Cn bng !5. )h8n 3ng oei ho( B 6ha
].1. C(! :nh nghR. &' !h9t oei ho( B 6ha
Cht oxi hoa la cht co kha nng nhn electron.
Cht khu la cht co kha nng cho electron.
Mt cht oxi hoa sau khi nhn electron s tro thanh cht khu gi la cht khu lin
hop cua no. Mi cp oxi hoa khu lin hop oc biu din bng phng trinh:
Ox ne
ed
Trong o Ox cht oxi hoa
ed cht khu
n s in tu ma cht oxi hoa nhn tro thanh cht khu.
Vi du cp oxi hoa khu lin hop:
Z$ng oei h-. Z$ng 6ha CV) oei h-. B 6ha
;iWn hP)
n
2
2e n
0
n
2
/ n
0
Fe
3
e Fe
2
Fe
3
/ Fe
2
2 H
2e H
2
2H
/ H
2
Cl
2
2e 2 Cl
-
Cl
2
/2Cl
-
MnO
-
e H
Mn
2-
H
2
O MnO
-
/ Mn
2-
Fe(CN)
3-
e Fe(CN)
-
Fe(CN)
3-
/ Fe(CN)
-
lectron khng tn tai o trang thai tu do trong dung dch. Mt cht chi th hin tinh
khu khi co mt cht oxi hoa nhn in tu cua no.
Phan ung oxi hoa khu la phan ung trao i in tu giua cht khu (cht cho
electron) va cht oxi hoa (cht nhn electron).
Hay noi mt cach khac: Phan ung oxy hoa khu la phan ung trong o co su thay i
muc oxi hoa, cht oxi hoa nhn electron va muc oxi hoa giam, cht khu nhong electron
va muc oxi hoa tng.
ed
1
Ox
1
e : su khu cht khu b oxi hoa
Ox
2
e ed
2
: su oxi hoa cht oxi hoa b khu
ed
1
Ox
2
Ox
1
ed
2
: qua trinh oxi hoa khu
Mt cht cang d nhn electron thi no co tinh oxi hoa cang manh, ngoc lai mt cht
nhong electron cang d thi no co tinh khu cang manh.
Trong mt cp oxi hoa khu lin hop, nu cht oxi hoa co tinh oxi hoa cang manh thi
cht khu co tinh khu cang yu va ngoc lai.
Vi du: a) Khi nhung mt thanh km vao dung dch CuSO
s xay ra phan ung oxi

hoa khu giua cac ion Cu
2
va cac nguyn tu n:
n
0
Cu
2
n
2
Cu
0
Cu
2
2e Cu
0
n
0
- 2e n
2
Trong o cac ion Cu
2
nhn e cua cac nguyn tu n, ta noi nguyn tu n b oxi hoa
thanh n
2
con ion Cu
2
b khu thanh nguyn tu Cu.
b) 2Fe 3Cl
2
2 FeCl
3
- Cht khu: Fe
- Cht oxi hoa: Cl
2
- Su khu Fe: Cl
2
0
2 e 2Cl
-
x3
- Su oxi hoa Cl
-
: Fe - 3e Fe
3
x2
Cng 2 qua trinh khu va oxi hoa: 2Fe 3Cl
2
2 FeCl
3
5n 6Ong phgn ]ng -Z h-+ kh/ #The- phKUng ph+p th$ng 6Ong e)
Nguyn tc: Tng electron ma cht khu nhong i bng tng electron
ma cht oxi hoa thu vao.
Cac boc:
a. ac nh cht oxi hoa, cht khu.
b. Thanh lp phng trinh electron
c. Cn bng phng trinh electron (Tim BSCNN cua tng thu va tng nhong
ri tim h s cn bng).
d. Hoan thin phng trinh phan ung.
Vi du:
Boc 1: Cht khu la As
2
S
3
; Cht oxy hoa la HNO
3
Boc 2 va 3: thanh lp phng trinh electron va cn bng:
Boc : hoan thin phng trinh phan ung
]./. Ph"%ng trfnh Ngrn@t &2 th? :i,n !A! tiWu !huhn
n
0
Cu
2
n
2
Cu
0
Cu
2
2e Cu
0
n
0
- 2e n
2
D chung minh co su dch chuyn electron tu cht khu la km sang cht oxi hoa la
ion ng ngoi ta thuc hin nh sau:
Co hai chic binh (l). L thu nht cho dung dch nSO
, l thu hai cho dung dch

CuSO
vao. Nng hai dung dch bng nhau. Nhung mt la Cu vao dung dch CuSO
,
mt la n vao dung dch nSO
. Ni hai dung dch bng mt hinh chu ung dung dch

Na
2
SO
(hoc KNO
3
). ng nay oc gi la cu mui. Thit b nay gi la pin in hoa
(pin ganvani).
Ni hai in cuc n va Cu bng mt dy dn, trn dy co mc ni tip mt vn k.
Hin tong quan sat oc:
- Kim in k quay. Chiu quay cua kim in k chung to xut hin dong in mt
chiu tu la Cu (cuc ) sang la n (cuc ) nhng chiu di chuyn cua dong electron mach
ngoai thi ngoc lai, tu la n (cuc ) sang la Cu (cuc ).
- Din cuc n b n mon dn
- Co mt lop kim loai ng bam trn in cuc Cu
- Mau xanh cua cc ung dung dch CuSO
b nhat dn.
- Sau khi kim in k tro v v tri O, em dung dch trong hai binh i phn tich ta
thy nng dung dch km tng ln, con dung dch ng giam i.
Giai thich:
Din cuc n b oxi hoa: n n
2
2e
Din cuc Cu b khu: Cu
2
2e Cu
n
0
Cu
2

n
2
Cu
0
Thi nghim trn chung to rng cht oxi hoa trong cp oxi hoa khu lin hop Cu
2
/Cu
co th oxi hoa cao hn nn oxi hoa cht khu thuc cp oxi hoa khu lin hop n
2
/n co
th thp hn.
hg thch h!n tKng cB. th ngh!%*
- Din cuc n b oxi hoa: n n
2
2e (su mt electron xay ra trn b mt la n va la n tro
thanh ngun electron nn ong vai tro cuc m, cac electron theo dy dn n cuc Cu). Do vy cuc n b
n mon.
- Trong cc ung dung dch CuSO
, cac ion Cu
2
di chuyn n la Cu, tai y chung b khu thanh Cu
kim loai bam trn cuc ng: Cu
2
2e Cu. Nng Cu
2
trong dung dch giam dn, khin cho mau
xanh trong dung dch nhat dn.
- Trong qua trinh hoat ng cua pin in hoa n Cu, nng ion n
2
trong cc ung dung dch
nSO
tng dn, nng ion Cu

2
trong cc kia giam dn. Dn mt luc nao o, dong electron trong dy
dn khng con, dong in tu ngt.
- D duy tri oc dong in trong qua trinh hoat ng cua pin in hoa, ngoi ta dung cu mui. Vai tro
cua cu mui la trung hoa in tich cua 2 dung dch: cac ion dng Na
hoc K
va n
2
di chuyn qua
cu mui n cc ung dung dch CuSO
. Ngoc lai , cac ion m SO
2-
hoc NO
3
-
di chuyn qua cu
mui n dung dch nSO
.
- O mach ngoai (dy dn), dong electron i tu cuc n sang cuc Cu con dong in i tu cuc Cu sang cuc
n. Vi th in cuc n oc gi la anot (ni xay ra su oxi hoa), in cuc Cu oc gi la catot (ni xay
ra su khu). 0I< trong )in :i,n h-., .not ;2 !A! 7 !1n !.tot ;2 !A! d"%ng.
Th oxi ha kh:
Kha nng cho hay nhn electron cua cac cht khac nhau thi khac nhau. D anh gia
kha nng cho/nhn electron (tinh cht oxi hoa khu) cua mt cht ngoi ta dung mt ai
long nhit ng gi la th oxi hoa khu cua cp oxi hoa khu lin hop. Vi du
,... ,
/ /
2 2
in in 5u 5u
E E
+ +
Th oxi hoa khu cua cp oxi hoa khu lin hop la ai long c trng cho kha nng
oxi hoa hay noi cach khac no la ai long c trng cho cong cht oxi hoa va cht
khu cua cp o. Th oxi hoa khu cua mt cp lin hop cang lon thi tinh oxi hoa cua cht
oxi hoa trong cp cang manh va tinh khu cua cht khu trong cp lin hop cang yu va
ngoc lai.
Trong hai cp oxi hoa khu lin hop, nu th cua cp thu nht lon hn th cua cp
thu hai thi cht oxi hoa cua cp thu nht manh hn cht oxi hoa cua cp thu hai, nhng
ngoc lai cht khu cua cp thu hai manh hn cht khu cua cp thu nht.
Th oxi hoa khu cua cp oxi hoa khu lin hop (Ox/ed):
Ox ne ed
oc xac nh bng phKUng trnh Xerst #Xec):
,
IZ
, IZ
.
.
nF
jT
E E
e
0
e /
ln +
Trong o:
th oxi hoa khu cua cp Ox/ed, Vont;
0
th oxi hoa khu tiu chun cua cp Ox/ed (khi hoat cua cht oxi hoa ca cht
khu u bng 1 mol/l, Vont;
hng s, ,31 J.mol
-1
.K
-1
;
T nhit tuyt i, K;
F s Faraday, F 00 Culong;
n s electron ma mt ion, phn tu hay nguyn tu trao i (cho hay nhn);
a
Ox
, a
ed
hoat cua cht oxi hoa va cht khu trong dung dch.
Tng quat, nu co phan ung:
pOx ne
qed
thi phng trinh Nerst:
2
,
p
IZ
, IZ
.
.
nF
jT
E E
e
0
e /
ln +
Nu co ion H
tham gia vao qua trinh oxi hoa khu thi gia tr cua th oxi hoa khu
khng nhung phu thuc vao hoat cua cht oxi hoa va cht khu ma con phu thuc vao
ca hoat cua ion H
:
2
,
%
J
p
IZ
, IZ
.
. .
nF
jT
E E
e
0
e /
ln
+
+
Khi thay ca , F bng gia tr tht cua chung, i logarit tu nhin sang logarit thp
phn thi o 2
0
C pt Nerst tro thanh:
2
,
%
J
p
IZ
, IZ
.
. .
n
E E
e
0
e /
ln
0 , 0 +
+
5hk l*
* hoat cua chn rn oc coi la bng 1. Nn i voi cp lin hop Cu
2
2e
Cu, pt Nerst s la:
+ +
+
2 2
ln
2
0 , 0
0
/ 5u 5u 5u
. E E
* Di voi cht khi, thay vi hoat ta dung ap sut p. Vi du:
Cl
2
0
2 e 2Cl
-
2
0
2 /
2
2
ln
2
0 , 0
+
5l
5l
5l 5l
.
p
E E
* hoat cua noc la mt hng s, nn oc a vao
0
. Vi du:
MnO
-
H
Mn
2
H
2
O
+
+
+
2
0
/ ,
ln
0 , 0
Sn
J SnI
Sn J SnI
.
. .
E E
* Trong phng trinh Nerst, ai long
0
la mt hng s, no chi phu thuc vao ban
cht cua h oxi hoa khu lin hop chu khng phu thuc vao nhit . Vi vy co th dua
vao th oxi hoa khu tiu chun
0
cua cac cp so sanh cong cua cht oxi hoa va
cht khu cua cac cp.
Vi du:
+
0
/
2
5u 5u
E
,
+
0
/
2
in in
E
Trn thuc t khng th xac nh oc gia tr tuyt i cua th oxi hoa khu cua cp
oxi hoa khu lin hop ma chi xac nh oc gia tr tng i cua no so voi th cua mt
cp khac. Vi vy so sanh th cua cac cp oxi hoa khu lin hop voi nhau thi cn phai
xac nh gia tr tng i th cua cp o so voi th cua mt cp oxi hoa khu lin hop
oc qui oc dung lam chun co gia tr th bng khng.
Ngoi ta qui oc th oxi hoa khu cua cp oxi hoa khu lin hop 2H
/H
2
bng 0 va
o th oxi hoa khu cua cac cp khac ngoi ta dung cuc hidro tiu chun.
Cu tao cua in cuc hiro chun: gm mt thanh platin (Pt) oc t trong mt
dung dch axit co nng ion H
la 1M (pH 0). B mt in cuc hp thu khi hiro,

oc thi lin tuc vao dung dch doi ap sut 1 atm. Nh vy trn b mt in cuc hiro
xay ra cn bng oxi hoa khu cua cp oxi hoa khu 2H
/H
2
:
H
2
i 2 H
2e
uy oc rng: th in cuc cua in cuc hiro chun bng 0,00 V o mi nhit ,
tuc la:
P E
J J
00 , 0
0
/ 2
2

+

Th oxi ha kh tiu chun ca kim loi
Ta dung th in cuc hiro chun
0
/ 2 J J
E
+ xac nh th in cuc chun cho cac cp
oxi hoa khu khac. Bng cach ni cp oxi hoa khu M
n
/M chun (cation M
n
co nng
1M, nhit 2
o
C) voi cp 2H
/H
2
chun. Th oxi hoa khu tiu chun cua kim loai
cn o oc chp nhn bng sut in ng cua pin tao boi in cuc hiro chun va in
cuc chun cua kim loai cn o. Co 2 trong hop xay ra voi gia tr cua th in cuc
chun:
- Th in cuc chun cua cp M
n
/M la s dng nu kha nng oxi hoa cua ion
M
n
trong nua pin M
n
/M la manh hn ion H
trong nua pin 2H
/H
2
2Fe
3
H
2

2Fe
2
2H
- Th in cuc chun cua cp M

n
/M la s m nu kha nng oxi hoa cua ion
M
n
trong nua pin M
n
/M la yu hn ion H
trong nua pin 2H
/H
2

2H
H
2
n
2
0* d4: Th oxi hoa khu tiu chun cua cac cp kim loai:
o
n
2
/n
0, V ;
o
Ag
/Ag

0,0 V.
5heu cB. phgn ]ng -Z h-+ kh/
D xet chiu cua phan ung oxi hoa khu, ta dua vao th in cuc chun
o
cua cac
cp. Cp nao co
o
lon thi dang oxi hoa cua cp o s oxi hoa dang khu cua cp co
th in cuc chun nho hn.
].3. C(! <?u tG 8nh h"bng :?n th? !n bng oe< h-. 6ha. Th? tiWu !huhn :i'u
6i,n
Th oxi hoa khu tiu chun la th khi hoat cua tt ca cac dang tham gia phan ung
bng 1M. Trong thuc t cht oxi hoa va cht khu cua mt cp oxi hoa-khu lin hop
thong tham gia phan ung phu voi cac cht co mt trong dung dch nh phan ung kt tua,
phan ung tao phuc, phan ung axit-baz, . Khin cho nng (hoat ) cua cac cht thay
i.
Trong iu kin nay, anh gia ung cong cht oxi hoa va cht khu ta dung
th oxi hoa khu tiu chun iu kin la th khi hoat cac dang oxi hoa, khu cua ban
phan ung u bng 1M va cac thanh phn khac cua ban phan ung co nng xac nh.
Tu cac gia tr
0
ta co th xac nh oc gia tr th tiu chun iu kin (
0,
) cua cac cp
oxi hoa khu o iu kin thi nghim xac nh.
cnh hKYng cB. pJ* Trong trong hop cp oxi hoa khu gm 2 anion co chua s
nguyn tu oxi khac nhau va H
tac dung ln anion co chua nhiu oxi nht (ung voi s oxi
hoa cao hn) tao ra anion co it oxy hn (ung voi s oxi hoa thp hn).
Vi du: Tinh th oxi hoa khu tiu chun iu kin khi pH .
AsO
3-
2 H
2e
AsO
3
3-
H
2
O
+
+ +
3
3
3
lg
2
0 , 0
lg
2
0 , 0
2 0
"sI
"sI
J
.
.
. E E
Th oxi hoa khu tiu chun iu kin khi pH la th khi:
1
3
3
3

"sI "sI
. .
,
[ ]
10
+

+
J .
J
. 11 , 0 ) 10 lg(
2
0 , 0
, 0
) 10 lg(
2
0 , 0
2 0
2 0 0
P E
E E
+
+
Nh vy, khi tng pH thi th th tiu chun giam, lam giam kha nng oxi hoa cua
AsO
3-
va lam tng kha nng khu cua AsO
3
3-
.
cnh hKYng cB. phgn ]ng t8- ph]c
Khi dang oxi hoa hoc dang khu cua mt cp lin hop tham gia vao phan ung tao
phuc, thi cong oxi hoa, khu cua chung cung thay i.
Vi du:
Tinh th oxi hoa khu tiu chun iu kin cua cp Fe()/Fe() trong iu kin khi
dung dch co d F
-
tao FeF
3-
co hng s bn tng cng
1..
10
1
. Th tiu chun cua
cp Fe()/Fe() khi chung khng co su tao phuc la
0
0, V.
Trong h kha nng xay ra 2 phan ung:
Fe
3
e
Fe
2
(khi khng co F
-
)
+
+
+ +
+
3
2
2 3
lg
1
0 , 0
0
/
Fe
Fe
Fe Fe
.
.
E E
(1)
Fe
3
F
-

FeF
3-
FeF
3-
1e
Fe
2
F
-
(khi co F
-
)
+
+
+ +
+
3
2
2 3
0
/
lg
1
0 , 0
FeF
F Fe
Fe Fe
.
. .
E E
(2)
1
1
3
3
+
+
+
+
F Fe
FeF
FeF
F Fe
. .
.
.
. .
(3)
Thay (3) vao (2), ta co:
1
0
/
0
/
3
2
2 3
3
2
2 3
lg
1
0 , 0
lg
1
0 , 0
+
+
+ +
+
+
+ +
F Fe
F Fe
Fe Fe
FeF
F Fe
Fe Fe
. .
. .
E E
.
. .
E E
+
+
+ +
+ +

3
2
2 3
lg
2
0 , 0
lg
1
0 , 0
1
0
/
Fe
Fe
Fe Fe
.
.
E E
()
0
/
1
0
/
2 3 2 3
lg
1
0 , 0
+ + + +
+

Fe Fe Fe Fe
E E
1
0
/
0
/
lg
1
0 , 0
2 3 2 3

+ + + +

Fe Fe Fe Fe
E E
Cng thuc chung
Khi Ox tham gia vao qua trinh tao phuc thi th oxi hoa khu iu kin s la:
) (
0
e /
0
e / ) (
lg
0 , 0
G IZ , IZ , G IZ
n
E E
Khi ed tham gia vao qua trinh tao phuc thi th oxi hoa khu iu kin s la:
) ( e
0
e /
0
) ( e /
lg
0 , 0
G , , IZ G , IZ
n
E E +
Khi ca Ox va ed tham gia vao qua trinh tao phuc thi th oxi hoa khu iu kin s
la:
) (
) ( e 0
e /
0
) ( e / ) (
lg
0 , 0
G IZ
G ,
, IZ G , G IZ
n
E E
+
cnh hKYng cB. phgn ]ng t8- kt tB.
Tng tu nh qua trinh tao phuc. Thu tinh th oxi hoa khu tiu chun iu kin cua
cp Cu()/Cu() khi co d anion
-
tao kt tua Cu voi ion Cu
, Cu co tich s tan
T
Cu
10
-12
. Th tiu chun cua cp Cu()/Cu() khi khng tao kt tua Cu la 0,1V.
Cu
2
1e
Cu
(khi khng co anion

-
)
+
+
+ +
+
5u
5u
5u 5u
.
.
E E
2
2
lg
1
0 , 0
0
/
(1)
Cu
2
1e
Cu
Cu
Cu
Cu
2

-
1e
Cu (khi co anion
-
)
+ + +
+
_ 5u 5u 5u
. . E E
2 2
lg
1
0 , 0
0
/
(2)
+

_ 5u
. . T
(3)
Thay (3) vao (2) ta co:
+
+
+ +
+ + +
+
+
5u
5u
5u 5u
_ 5u 5u 5u
.
T .
E E
. . E E
2
2
2 2
lg
1
0 , 0
) lg(
1
0 , 0
0
/
0
/
+
+
+ +
+ +
5u
5u
5u 5u
.
.
T E E
2
2
lg
1
0 , 0
lg
1
0 , 0
0
/
()
So sanh (1) va () ta co:
T E E
E T E
5u 5u 5u 5u
5u 5u 5u 5u
lg
1
0 , 0
lg
1
0 , 0
0
/
0
/
0
/
0
/
2 2
2 2

+
+ + + +
+ + + +
Cng thuc chung
Khi Ox tham gia vao qua trinh tao cht kt tua thi th oxi hoa khu iu kin s la:
) (
0
e /
0
e / ) (
lg
0 , 0
" IZ , IZ , " IZ
T
n
E E +
Khi ed tham gia vao qua trinh tao cht kt tua thi th oxi hoa khu iu kin s la:
) ( e
0
) ( e /
0
) ( e /
lg
0 , 0
" , " , IZ " , IZ
T
n
E E
Khi ca Ox va ed tham gia vao qua trinh tao cht kt tua thi th oxi hoa khu iu
kin s la:
) ( e
) ( 0
e /
0
) ( e / ) (
lg
0 , 0
" ,
" IZ
, IZ " , " IZ
T
T
n
E E +
].O. 0In tG! )h8n 3ng. C(! <?u tG 8nh h"bng X TH
].[. cng d4ng )h8n 3ng oei ho( 6ha trong h-. )hn t*!h B TH
j. C(! )h8n 3ng ion trong dung d!h n"#!
j.1. NhUng d9u hi,u :V! tr"ng !5. )h8n 3ng ion trong dung d!h n"#!
Cac phan ung ion trong dung dch noc co th xay ra o muc ang k nu san
phm phan ung thuc loai hop cht:
- it phn li
- it tan
- d bay hi hn cac cht ban u
- ca ion co trang thai oxi hoa khac voi cac cht ban u.
Dua vao nguyn tc nay ta co th phn loai cac phan ung ion sau y:
a) - Phan ung giua acid va baz:
HCl NaOH NaCl H
2
O
PT ion: H
OH
-
H
2
O
Cht it phn li la noc.
CH
3
COOH NH
3

CH
3
COONH
PT ion:
CH
3
COOH
CH
3
COO
-
H
NH
3
H
NH
CH
3
COOH NH
3

CH
3
COO
-
NH
Cht it phn li la NH
(acid cation)
- Phan ung giua oxit baz voi axit, oxit axit voi baz kim.
CuO HCl CuCl
2
H
2
O
PT ion:
CuO 2 H
Cu
2
H
2
O
CO
2
2 NaOH Na
2
CO
3
H
2
O
PT ion: CO
2
2 OH
-
CO
3
2-
H
2
O
- Phan ung giua mui axit yu voi axi manh hn, giua mui ba yu voi baz manh
hn.
CH
3
COONa

HCl CH
3
COOH NaCl
PT ion: CH
3
COO
-
H
CH
3
COOH
Cht it phn li la CH
3
COOH.
NH
Cl NaOH NaCl NH
3
H
2
O
PT ion: NH
NH
3
H
OH
-

NH
3
H
2
O
NH
OH
-

NH
3
H
2
O
b) Phan ung tao phuc:
c) Phan ung oxi hoa khu:
d) Phan ung tao thanh cht it tan:
j./. C(! h, thGng )hn t*!h !.tion &2 .nion trong dung d!h n"#!
`hgn ]ng h! th=ng* tu dung dch u ta ta ln lot tach ra tung nhom ion ring bit
bng cach su dung nhung thuc thu nhom thich hop. Sau o su dung cac phan ung c
trng tim ion trong mi nhom theo mt trinh tu nht nh. Co th tach cac ion trong
mt nhom.
`hn tch rmng 6!t* xac nh truc tip mt ion trong hn hop nhiu ion bng mt
phan ung c trng phan ung xay ra voi ring ion o. Mi ion oc tim thoe mt qui
trinh ring, thu tu khng quan trng. Thng thong moi u ta thuc hin mt phan ung
tach nhom thich hop: ion cn tim co th nm trong dung dch noc lc hoc trong kt tua.
Du trong pha nao thi no cung ln voi mt s ion khac nhng chung khng gy nhiu khi
ta nhn bit ion phai tim bng mt phan ung c hiu cho ion o.
Phan ung c trng cua mt ion la phan ung cho phep nhn bit ich thuc ion y
trong su co mt cua mt t hop nht nh ion khac.
ThuG! tha nh-7E La thuc thu tac dung ging nhau ln mt nhom cac ion.
Vi du: HCl la thuc thu cua nhom Ag
, Hg
2
2
, Pb
2
ThuG! tha !hkn ;k!E la thuc thu tac dung ging nhau trn mt s ion ma cac ion
nay co th thuc cac nhom phn tich khac nhau.
Vi du: NH
3
co th tao phuc tan va khng mau voi mt s ion o nhiu nhom phn
tich.
ThuG! tha :V! tr"ng h.< thuG! tha riWngE la thuc thu chi cho phan ung c hiu
voi mt ion hoc mt cht xac nh.
Vi du: NH
3
la thuc thu c trng phat hin Hg
2
2
trong nhom Ag
, Hg
2
2
, Pb
2
nho tao ra kt tua mau en c trng.
H tinh bt cho mau xanh chi voi iod.
`hn tch @nh tnh c.t-n* co hai h thng phn tich, o la pp dung H
2
S va pp acid
baz.
X H, thGng H
/
DE
Nguyn tc: dua trn su khac nhau v tan cua nhiu sunIid kim loai tach cac
cation thanh nhom.
u im: khac ht ch, kt qua kha chinh xac, phat hin trit cac cation k ca khi
chung nm trong phuc cht.
Nhoc im: H
2
S rt c hai, mui kho chu va trong qua trinh phn tich thong gp
cac dung dch keo cua S rt kho xu ly.
H, thGng .!id B b.QE
Nguyn tc: dua trn kha nng tao kt tua, tao phuc voi cac thuc thu acid nh HCl,
H
2
SO
, NaOH, (NH
)OH.
u im:
- it c hai hn h thng dung H
2
S.
- du dung oc nhung tinh cht c ban cua cac nguyn t: qun h cac nguyn t
nay voi cac acid va baz, tinh lng tinh cua cac hydroxyd va kha nng ta phuc cua cac
nguyn t.
- thoi gian thuc hin phn tich ngn hn tu 30-0 so voi h thng H
2
S.
Nhoc im: phn tich nhom khng cht ch bng h thng dung H
2
S.
Con gioi han v s long cac cation, cac tinh cht cua cac hydroxit cua cac cation
nhom va cha oc nghin cuu ki, cung nh iu kin tach, tao kt tua cua chung.
STT
nhom
Thuc thu
nhom
Cac cation thuc nhom San phm tao thanh voi thuc thu
nhom
HCl Ag
, Hg
2
2
, Pb
2
AgCl Hg
2
Cl
2
, PbCl
2
H
2
SO
long Ba
2
, Sr
2
, Ca
2
, (Pb
2
) BaSO
, SrSO
, CaSO
, (PbSO
)
NaOH d
H
2
O
2
Al
3
, Cr
3
, n
2
, Sn
2
,
Sn
, As
3
, As
AlO
2
-
, CrO
2-
, nO
2
2-
, SnO
3
2-
, AsO
3-
V NaOH Fe
2
, Fe
3
, Sb
3
, Sb
,
Bi
3
, Mn
2
, Mg
2
Fe(OH)
2
, Fe(OH)
3
, Sb(OH)
3
, Sb(OH)
,
Bi(OH)
3
, Mn(OH)
2
, Mg(OH)
2
,
V NH
OH c,
d
Cu
2
, Cd
2
, Hg
2
, Co
2
,
Ni
2
Cac phuc amino Me(NH
3
)
n
2
, n,
V Khng co Na
, K
,
NH
X H, thGng )hot)h.t .77oni.!E

`hn tch @nh tnh .n-n*
Do khng co thuc thu nhom r rang nn cung khng th phn chia mt cach cht
ch toan b cac anion thanh nhung nhom ring phn tich h thng ging nh cac
cation.
j.3. Phn t*!h !.tion nh-7 1,/,3 trong dung d!h n"#! thgo h, thGng .!id B b.Q
ac nh cac cation nhom 1 (Ag
, Pb
2
, Hg
2
2
):
ac nh cac cation nhom 2 (Ba
2
, Sr
2
, Ca
2
):
ac nh cac cation nhom 3 (Al
3
, n
2
):
Thuc thu Cation
Al
3
n
2
NaOH d AlO
2
-
nO
2
-
Na
2
CO
3
Al(OH)
3
keo trng n
2
(OH)
2
CO
3
trng
NH
OH d Al(OH)
3
keo trng n(NH
3
)
2
tan
Na
2
HPO
AlPO
trng n
3
(PO
)
2
trng
H
2
S trong CH
3
COOH - nStrng
(NH
)
2
S

trong mi trong
trung tinh hay kim yu
Al(OH)
3
keo trng nStrng
Phn /. C(! )h"%ng )h() )hn t*!h :nh ;"Png h-. hk!
/.1. $i !"%ng &' )hn t*!h :nh ;"Png
2.1.1. Phn bit phn tich nh tinh va phn tich nh long
Hoa hc phn tich nh tinh dung nhn bit mt cht hoc cu tu chua trong mt
hn hop (vi du xac nh trong mt hop kim co chua cac kim loai va phi kim nao).
Hoa hc phn tich nh long xac nh ham long mi cu tu trong mt hop cht
hoc mt hn hop.
Hoa hc phn tich nh tinh lun lun i troc giup ta bit oc mt cach ban
nh long (cu tu co nhiu hay it) thanh phn mt hn hop nho o ta co th chn quy
trinh phn tich nh long thich hop.
Hoa hc nh long oi hoi nhung dung cu, thit b, phng phap lam cht ch va
phuc tap hn.
Vi du: cho mt hn hop trong o co chua mt s kim loai.
Dnh tinh: ac nh cac kim loai o la nhung kim loai nao.
Dnh long: ac nh thanh phn khi long cua cac kim loai, thanh phn khi
long cua cac kim loai trong hn hop.
2.1.2. Phn loai cac phng phap phn tich nh long
nu+ trnh phn tch eu 6.- go% c+c g. -8n cU 6gn s.u
- Chn mu ai din (chn mt phn nho mu ai din cho toan b i tong
cn phn tich), cng vic nay cn phai oc quy hoach troc.
- Chuyn cht phn tich v dang dung dch: hoa tan hoan toan mu trong dung
mi thich hop. Nu phn tich bng mt s phng phap vt ly thi co th khng cn hoa
tan mu nhng cn phai xu ly hoa hc troc.
- Tach hoc che cac cu tu can tro cu tu chinh nu cn (dung phng phap hoa hc,
hoa ly, vt ly). Vi du: xac nh Ni
2
co mt Fe
2
bng dimetylglioxim thi cn chuyn
Fe
2
thanh Fe
3
sau o che Fe
3
bng F
-
o dang FeF
3-
.
- Tin hanh xac nh ham long mi cu tu bng phn tich theo phng phap
chn.
- Tinh toan kt qua (anh gia kt qua va chinh xac phn tich).
Trong cac giai oan nay thi giai oan 3 va la quan trng nht.
`hn l-8 c+c phKUng ph+p phn tch @nh lKng
Ham long cht (mg) K thut phn tich
1-10 (long nho) Phn tich dung cu
10
-3
(vt)
100 (long lon) Phn tich hoa hc
1-100 (ban vi)
Phng phap phn tich hoa hc: Cac phng phap nay khng oi hoi thit b phuc
tap (chi dung chu yu la cac dung cu thuy tinh).
D nhay khng cao nhng ap ung mt s yu cu thuc t.
Co 2 dang: phn tich khi long va phn tich th tich.
- phn tich khi long: dua vao vic cn san phm tao thanh sau qua trinh thuc
hin phan ung tao kt tua tu o xac nh ham long cu tu cn phn tich.
Cht khao sat oc hoa tan trong dung mi thich hop (thong la trong acid) ri dung
mt thuc thu tao mt hop cht it tan. Sau o em kt tua rua sach, nung n khi long
khng i, em cn. Tu khi long cht em cn va dua trn cng thuc cua cht y ta
tinh oc khi long cht khao sat.
Vi du: xac nh Fe() bng cach kt tua doi dang hidroxid va em nung tao
Fe
2
O
3
. Tu khi long Fe
2
O
3
suy ra khi long Fe.
Nhoc im cua pp:
Ham long cht phn tich phai kha lon, mt nhiu thoi gian.
- phng phap phn tich th tich: Dua vao vic o chinh xac th tich dung dch
thuc thu co nng chinh xac cung voi cht chi th i mau khi phan ung kt thuc
tinh ham long cu tu cn phn tich.
Phng phap phn tich th tich ap dung cho nhiu loai phan ung:
- chun axit baz;
- chun phuc cht;
- chun trm hin (kt tua);
- chun oxi hoa khu.
Cac phng phap phn tich cng cu
Cac phng phap vt ly: dua trn vic o mt tinh cht vt ly nao o ( hp thu anh
sang, dn in, in th, cong dong, cong buc xa in tu,...) ma tinh cht nay
ti l voi ham long cu tu cn phn tich. Vi du: xac nh ham long Bi
3
co th o
hp thu anh sang Bi
3
o boc song 0 nm vi cong mau cua dung dch nay ti l thun
voi nng cua no.
Cac phng phap hoa ly: trong nhiu trong hop, phan ung hoa hc ong vai tro rt
quan trng chuyn cu tu phn tich thanh dang co tinh cht vt ly co th o oc. Vi
du: nh long Fe
3
: dung thuc thu axit sunIosalixilic trong mi trong amoniac
chuyn v dang phuc Fe(Ssal)
3
3-
mau vang, o hp thu tu o xac nh oc nng
cua Fe
3
.
Hai yu t quan trng phn loai cac phng phap phn tich la: kich thoc mu
thu va ham long phn trm cua cu tu cn phn tich.
- Mu ban vi: 0,01-0,1g; mu vi long: 0,001-0,01g; mu siu vi long 0,001g.
- Cu tu lon: 1-100; be: 0,01-1 va vt0,01.
2.1.3. Cac loai nng va n v thong dung biu din kt qua phn tich
2.1.3.1. Cac loai nng
Nng dung dch la: long cht tan trong mt n v th tich hay mt n v khi
long.
Nng th tich cua mt cht long la ti s th tich cua cht long o va th tich cua
dung mi (thong la noc).
Nng khi long (C): chi ra co bao nhiu gam cht tan trong 100 g dung
dch.
100
,,
ct
%
%
5
Nng phn triu (ppm: parts per million): la s gam cht tan co trong 1 triu gam dung
dch hay khi long mg cht tan co trong 1 kg dung dch hay khi long g cht tan
trong 1 gam dung dch.
pp%
%
%
5
,,
ct
pp%
10
Nng phn ti (ppb: parts per bilion): la s gam cht tan co trong 1 ty gam dung dch
hay khi long g cht tan co trong 1 kg dung dch hay khi long ng cht tan trong 1
gam dung dch. Do dung dch rt long nn d1, va nng phn ti cung chinh la khi
long g co trong 1 lit dung dch.
pp6
%
%
5
,,
ct
pp%
10
Nng mol (ky hiu la C
M
, mol/l, M) la s mol cht tan trong 1 lit dung dch.
,,"
"
S
P
n
5
D chun T la s gam (hay miligam) cht tan trong 1mililit dung dch.
Cng thuc tinh :
P
.
T
a: s gam cht tan, V: th tich dung dch ml
D chun (A) theo cht oc xac nh (cht nh phn): la gam cht nh phn B tac
dung voi lu dung dch chun A. Vi du, AgNO
3
/Cl
-
T 0,00 (g/ml) nghia la 0,00g cht nh phn Cl
-
tac dung vua u voi lu dung dch
chun AgNO
3
.
Dng long: "%ng ;"Png !5. 1 ngu<Wn tG
.) ?KUng lKng cB. %9t nguymn t= l< lKng cB. n kt hp 1f & %-l nguymn
t/ hy,r- h.y th.y th %9t lKng nguymn t/ hy,r- nhK th tr-ng phgn ]ng
h-+ hpc.
6) ?KUng lKng cB. hp ch[t l< lKng ch[t n t+c ,0ng 1q. B 1f %9t KUng
lKng hy,r- h.y 1f %9t KUng lKng cB. %9t ch[t 6[t kr.
Nguyn t / hop cht z Dng long gam P ,0*
Nguyn t trong hop
cht voi H: AH
m
hoa tr cua nguyn
t: m
DM/m J
E
a* >:EM 7:FCsE
J5l* >:&M 7:FtMTs&
Oxit
A
2
O
n
Tng h-+ tr@ cB.
k% l-8sph k%* En
7:S
-Zt
sEn Fe
E
I
F
*
>:E.F:t
7:&tQst
Axit a= nguymn t/ J
Kc th.y th
7:S
.Zt
s> J
F
`I
C
* >:FM
7:D'sF
Baz a= nh% IJ Kc
th.y th
7:S
6.>
s> 5.#IJ)
E
* >:EM
7:(CsE
Mui Tng h. tr@ cB.
nguymn t/ k% l-8
7:S
%u=
s> 4.5l
E
* * >:EM
7:EQ'sE
Cht oxi hoa / cht
khu
a= electr-n %< %9t
phn t/ h-uc -n
tr.-
7:S
Iv
s>
7:S
je,
s>
c) uy oc ky hiu ng long cua nguyn t i la i.
Vd:
Trong hop cht :
HCl: ng long cua clo: 1mol
H2S: ng long cua lu huynh :1/2mol
CH: ng long cua cacbon:1/mol
NH3:ng long cua nit:1/3mol
Khi long cua 1 ng long nguyn t gi la khi long tng ng .
Vd:
Khi long tng ng cua Cl , S , C , N trong vi du trn la:
Cl : 3, ; S : 32/21 ; C : 12/3 ; N : 1/3, g/mol
Bn canh khi long tng ng i khi ngoi ta con a ra dung khai nim th
tich tng ng nghia la th tich ma mt ng long cua cht khao sat chim o
mt iu kin cu th.
Vi du : -Th tich tng ng cua H2 la 11.2 l/mol
-Th tich tng ng cua O2 la . l/mol
(et o iu kin tiu chun)
?KUng lKng g.% cB. %9t ch[t#nguymn t= h.y hp ch[t) l< lKng ch[t 6u th@
the- g.% c tr@ s= 6Ong tr@ s= KUng lKng ch[t .
DM/z
Vd:
Dng long gam cua hydro la:1,00
Dng long gam cua Ca
3
(PO
)
2
la:1,
Vd:
NaOH0. Ta co p/:
2NaOH H2SO Na2SO 2H2O
Tinh oc:(H2SO).
Cach tinh khi long tng ng cua mt s hop cht:
"%ng ;"Png !5. 7Ct oeit 6i7 ;o$i bng trkng ;"Png )hn ta !5. oeit !hi. !ho
tlng ho( tr !5. 6i7 ;o$i trong !`ng th3! oeit :-.
Vd: ng long Fe2O3:10/3x22,
"%ng ;"Png !5. 7Ct .eit bng trkng ;"Png )hn ta !5. .eit !hi. !ho @G ngu<Wn
ta H :"P! th.< th? trong )hn ta .eit :-.
Vd: ng long cua H3PO: /332,.
m"%ng ;"Png !5. 7Ct b.Q% bng trkng ;"Png )hn ta b.Q% !hi. !ho ho( tr !5.
ngu<Wn ta 6i7 ;o$i trong )hn ta b.Q% :-.
Vd: ng long cua Ca(OH)2:/23
"%ng ;"Png !5. 7Ct 7uGi bng trkng ;"Png )hn ta 7uGi !hi. !ho tlng ho( tr
!5. 6i7 ;o$i trong )hn ta 7uGi :-.
Vd: ng long cua Ca3(PO)2: 310/3x21,.
"%ng ;"Png !5. 7Ct !h9t oei h-. hoV! 7Ct !h9t 6ha trong )h8n 3ng oei h-.
6ha bng 6hGi ;"Png 7o; !5. !h9t :- !hi. !ho @G g;g!tron 72 7Ct )hn ta hoV! ion
!h9t :- tr.o :li.
Nm 12 nha khoa hc ngoi Anh la (Dalton) Dan -Tn a ra ng lut ng long
nh sau:
'C(! ngu<Wn tG 6?t hP) &#i nh.u h.< th.< th? !ho nh.u (trong )h8n 3ng ho(
hk!) thgo !(! 6hGi ;"Png tn ;, &#i t"%ng ;"Png !5. !hong.p
D d dang trong tinh toan ngoi ta co cach trinh bay khac:
'Cac khi long (cac th tich)cua cac cht phan ung voi nhau ti l voi cac khi long
(th tich)tng ng cua chung.
Nng ng long (C
N
, N): Nng ng long cua mt cht la s mol ng
long cua cht o trong mt lit dung dch hoc s milimol cua cht o trong mt ml dung
dch.
Nng ng long gam/lit, con gi la nng ng long, ky hiu la C
N
la s
ng long gam cht tan trong mt lit dung dch.
,,"
"
X
P
5

"
"
"
7
%

: s ng long gam cht tan A
i
S
7
"
"

: ng long gam cht A.
S z oc xac nh nh sau:
- trong phan ung oxi hoa khu: s z la s electron n ma mt phn tu
hoc mt ion o trao i.
- trong phan ung trung hoa: z la s H
hoc s OH
-
trong phn tu
acid/baz tham gia phan ung.
Dng long: "%ng ;"Png !5. 1 ngu<Wn tG
,) ?KUng lKng cB. %9t nguymn t= l< lKng cB. n kt hp 1f & %-l nguymn
t/ hy,r- h.y th.y th %9t lKng nguymn t/ hy,r- nhK th tr-ng phgn ]ng
h-+ hpc.
uan h giua cac nng :
Chuyn i giua C
M
, va C:
"
S
S
, 5
5
. . 10
Chuyn i giua C
M
, va C
N
:
>
5
5
X
S

Chuyn i giua C
M
, va C:
"
X
7
, 5
5
. . 10
2.1.3.2. Cac n v thong dung biu din kt qua phn tich

/.1.O. Ph. !h? dung d!h
2.1..1. Pha dung dch co nng mol/l (C
M
)
`h. ,ung ,@ch tq ch[t rwn tnh th*
D pha V(ml) dung dch A co nng C
M
tu tinh th rn co tinh khit p thi
khi long cht rn cn ly la:
10
) (
) (
p
S %l P 5
g %
" S
`h. l-xng %9t ,ung ,@ch the- nong 9 %-l ch- trKfc
Ap dung cng thuc
0
0
0
0
S
S
S S
5
P 5
P
P 5 P 5

D pha V(ml) dung dch A co C
M
tu dung dch A co C va d(g/ml). Th tich dung
dch A ban u cn phai ly bng:
10
) (
0
5 p
S %l P 5
P
" S

Vi du: Tu mui CuSO
, noc ct va cac dung cu cn thit, hy tinh toan va nu cach

pha ch 0 ml dung dch CuSO
1M.
S mol cht tan la:
4
CuSO M
n C .V 1.0,05 0,05(mol)
Khi long CuSO
co trong 0,0 mol CuSO
la:
4
CuSO
m
n.M 0,0.10 (g).
Cach pha ch: Cn g CuSO
cho vao cc thuy tinh dung tich 0ml. D dn dn

noc ct vao cc va khuy nhe cho u 0 ml dung dch. Ta oc 0 ml dung dch CuSO

1M.
Cng thuc chung, khi long cht co khi long mol M cn thit iu ch V (lit)
dung dch la:
mC
M
.V.M
`h. l-xng %9t ,ung ,@ch the- nong 9 %-l ch- trKfc
Ap dung cng thuc
0
0
0
0
S
S
S S
5
P 5
P
P 5 P 5

C
M1
V
1
C
M2
V
2
C
1
, V
1
: nng mol va th tich dung dch troc khi pha long
C
M2
, V
M2
: nng mol va th tich dung dch sau khi pha long
D pha V(ml) dung dch A co C
M
tu dung dch A co C va d(g/ml). Th tich dung
dch A ban u cn phai ly bng:
10
) (
0
5 p
S %l P 5
P
" S

Vi du: pha ch 100ml dung dch MgSO
0, M tu dung dch MgSO

2M.
Ap dung cng thuc: C
1
V
1
C
2
V
2
Ta co: 0,1 x 0, 2 x V
1
V
1
0,02 l
Ly 20ml dung dch MgSO
cho vao cc thuy tinh 200ml. D tu tu noc ct vao

cc va khuy nhe n 100ml thi dung lai. Doc 100ml dung dch MgSO
0,0M.
2.1..2. Pha dung dch co nng ng long C
N
?= 1f ch[t rwn*
D pha V(ml) dung dch A co nng C
N
tu tinh th rn co tinh khit p thi khi
long cht rn cn ly la:
10
) (
) (
p
S %l P 5
g %
" X
?= 1f ,ung ,@ch*
Pha dung dch A co C
N
tu:
- dung dch co nng mol C
N
0
(pha long):
0 0
0
0
X
X
X X
5
P 5
P
P 5 P 5

- tu dung dch A co C va d(g/ml). Th tich dung dch A ban u cn phai
ly bng:
10
) (
0
5 p
S %l P 5
P
" X

`h. ch ,ung ,@ch tq %u= rwn tnh th

Cach tin hanh va tinh toan tng tu nh khi iu ch dung dch co nng mol/l.
Nhng thay vi M dung khi long ng long (ng long gam D). Khi long cht
cn dung la:
mC
N
.V.D
`h. l-xng %9t ,ung ,@ch the- nong 9 KUng lKng C
N1
ch- trKfc
Ap dung cng thuc
C
N1
V
1
C
N2
V
2
2.1..3. Pha dung dch co nng phn trm th tich (C)
D pha V
1
(ml) dung dch A co C
1
va d
1
(g/ml) tu dung dch m c co C
2
va
d
2
(g/ml), th tich dung dch ban u cn dung V
2
:
2 2 2 1 1 1
, 5 P , 5 P
2 2
1 1 1
2
, 5
, 5 P
P
2.1... Pha dung dch co nng phn trm khi long

Di voi cht rn khng ngm noc:
D pha m
dd
(g) dung dch A co C tu tinh th rn khng ngm noc co tinh khit
p thi khi long cht rn cn ly la:
p
% 5
%
,,
Di voi cht rn ngm noc:

2
1
S
S
p
% 5
%
,,
Pha dung dch co nng phn triu C

ppm
D pha V (ml) dung dch A co nng phn triu C
ppm
tu tinh th rn A co tinh
khit p thi khi long cht rn cn ly la:
) ( 10
) (
g
S
S
p
5 %l P
%
-n
"
pp%

A co C tu tinh th rn khng ngm noc co tinh khit p thi khi long cht
rn cn ly la:
`h. ch ,ung ,@ch tq %u= rwn tnh th
* Pha dung dch cht co M, khi long dung dch m
dd
, nng phn trm C
100
,,
ct
% 5
%

ct ,, ,%
% % %
Tu mui CuSO
, noc ct va cac dung cu cn thit, hy tinh toan va nu cach pha

ch 0 gam dung dch CuSO
10.
Khi long cht tan la:
4
dd
CuSO
C%.m 10.50
m 5(g)
100% 100

Khi long dung mi la:
m
dm
m
dd
m
ct
0 (g)
Cn g CuSO
khan cho vao cc 100ml. Cn ly g noc ct, ri dn vao cc

va khuy nhe. Doc 0g dung dch CuSO
10.
* Pha dung dch cht co M, V (ml) dung dch co khi long ring d (g/ml), nng
phn trm C.
P , %
,,

100
,,
ct
% 5
%

ct ,, ,%
% % %
`h. l-xng %9t ,ung ,@ch the- phWn tr$% kh= lKng 5
&
y

Vi du: pha ch 10g dung dch NaCl 2, tu dung dch NaCl 10.
Khi long NaCl trong 10g dung dch NaCl 2,:
dd
NaCl
C%.m 2,5.150
m 3,75(g)
100% 100

Khi long dung dch NaCl 10 chua 3,g NaCl:
ct
dd
m .100% 3,75.100
m 37,5(g)
C% 10

Khi long noc cn dung:
m
dm
10 3, 112,(g)
Cach pha ch: Cn ly 3,g dung dch NaCl 10 cho vao cc thuy tinh 200ml.
Cn tip ly 112,g noc ct(hoc ong 112,ml) tu tu vao cc ung dung dch NaCl
10, khuy u. Ta oc dung dch NaCl 2,.
`h. l-xng %9t ,ung ,@ch the- phWn tr$% kh= lKng 5
&
y

1< kh= lKng rmng ,
&
ch- trKfc
V
1
x C
1
x

d
1
V
2
x C
2
x

d
2
Vi du: pha 1 lit dung dch H
2
SO
co d
2
1g/ml tu dung dch m c co d
1
1, g/ml.
V
1
x C
1
x

d
1
V
2
x C
2
x

d
2
V
1
x x 1, 1 x x 1
V
1
2,3 ml.
2.1... Pha dung dch co nng C
ppm
pp%
%
%
5
,,
ct
pp%
10
10
,, pp%
ct
% 5
%

/.1.[. qa ;> thGng 6W !(! 6?t ru8 thA! nghi,7

Trong phn tich vic anh gia cac kt qua la mt trong nhung boc khng th thiu
oc cua cac qua trinh phn tich. Trong boc nay vic tinh sai s la quan trng nht vi no
cho ta bit kt qua phn tich thu oc ung va chinh xac toi muc nao.
Gia su chung ta tin hanh xac nh mt ai long nao o n ln bng mt quy trinh
phn tich duy nht (ta noi phep xac nh oc lp lai n ln), cho ta cac kt qua tng ung
x
1
, x
2
, x
3
. x
n
. Gia tr trung binh s hc Z , thong khac voi gia tr thuc cua ai long
cn xac nh:
n
Z Z Z
Z
n
+ + +
...
2 1
2.1..1. Sai s o long, phn bit SSNN va SSHT ui tc CSCN
a. s= h! th=ng hoc sai s xac nh la nhung sai s do nhung nguyn nhn c nh
gy ra, lp i lp lai, khng phu thuc vao khng gian, thoi gian va ngoi lam thi nghim,
vi vy no lun co du hoc lun co du -.
Sai s h thng co th do phng phap lua chn khng phu hop, do dung cu o
long dung trong thi nghim nh cn, dung cu o th tich nh buret, pipet hoc binh nh
muc khng ung th tich trn vach chia; do hoa cht khng tinh khit; do xac nh nng
dung dch chun sai; do ngoi tin hanh phn tich khng co k nng ngh nghip
thiu kinh nghim phn tich).
Sai s h thng d phat hin va cung d tim oc nguyn nhn khc phuc bng
nhung bin phap thich hop nh sua chua hiu chinh dung cu may moc, pha lai va kim
tra lai cac dung cu, dung dch chun va iu ch lai hoa cht dung lam thuc thu v..v.
a. s= ngzu nhmn la nhung sai s gy nn boi nhung nguyn nhn khng c nh,
khng bit troc, thay i khng theo quy lut, khi dng, khi m. Nguyn nhn gy nn
sai s ngu nhin co nhiu nh: do ngoi phn tich mt luc nao o thiu tp trung hoc
tin hanh thao tac i khi thiu cn thn, su thay i v nhit , ap sut khi quyn ni
lam phn tich, khng khi b nhim bn, .
Di voi cac sai s ngu nhin ta khng th bit troc loai tru cac nguyn nhn
gy ra no ma chi c gng giam sai s o toi muc ti thiu bng cach phn tich tht cn
thn va tng s ln phn tich ri cui cung su ly cac s liu bng phng phap thng k
toan hc.
ChU @G !- nghR. &2 !(!h ghi 6?t ru8 )hn t*!h
ChU @G !- nghR.
Kt qua cua mt phep o truc tip cung nh cua mt thao tac phn tich phai oc
ghi chep sao cho ngoi su dung s liu hiu oc muc chinh xac cua phep o. Vi vy
ngoi ta quy nh vic biu din kt qua cua phep o theo ung quy oc v chu s co
nghia.
Chu s co nghia bao gm cac chu s tin cy cung voi chu s bt nh (khng tin
cy). V nguyn tc, s liu phai oc ghi sao cho chu s cui cung la bt nh.
VD: 1, 2 3 : chu s co nghia, chu s tin cy (1,2,3,), 1 chu s bt nh
()
Nu cn trn cn phn tich voi nhay + 0,1mg thi kt qua phai oc ghi n
chu s chi phn moi mg.
Vi du: 1,2 gam ma khng ghi la 1, gam hay 1,2 gam, trong o cac
chu s 1, , , 2 la cac chu s hoan toan tin cy vi ta c oc tu qua cn, con chu
s la bt nh vi oc ghi oc tinh trn thang chia. Trong kt qua cn nay, ta co
chu s co nghia gm chu s tin cy (cac chu s 1, , , 2) va 1 chu s bt nh
(chu s ).
Khi c th tich ghi trn buret oc chia n 0,1ml thi kt qua phai oc
ghi n chu s chi phn trm ml vi phn moi ml la s chc chn (tin cy), con phn
trm ml la s ghi ngo (bt nh).
Vi du: phai ghi V 12,ml ma khng ghi 12,ml hay 12,ml.
Di voi chu s 0: khng oc tinh la s co nghia khi no oc dung thit
lp im thp phn, con chu s 0 ung giua hoc ung sau cac chu s khac thi oc
tinh vao s co nghia. Vi du: s 0,02030 thi hai chu s 0 ung troc s 2 khng oc
tinh la s co nghia, hai chu s 0 con lai la s co nghia, s nay co chu s co nghia
(2, 0, 3, 0) trong o 2, 0, 3 la s tin cy va 0 (chu s cui cung) la s bt nh.
Di voi cac s phuc tap ngoi ta thong chuyn sang dang s luy thua thp
phn thi cac s o phn nguyn oc tinh vao chu s co nghia, con bc luy thua
khng oc coi la chu s co nghia.
Vi du: 10 1,0.10
3
co chu s co nghia; 0,0000 ,0.10- co 3 chu
s co nghia; 2, gam co 2 chu s co nghia va nu quy ra mg thi phai vit 2,.103mg
( co 2 chu s nghia) ma khng oc vit la 200mg (co chu s co nghia).
Di voi cac s logarit thi cac chu s o bn trai im thp phn (phn nguyn)
khng oc coi la s co nghia. Vi du: lgx 3, x 10
0,
.10
3
co 2 chu s co
nghia (chu s va ) con chu s 3 la bc cua luy thua.
Tu< ts! ;27 tr1n @G
Kt qua tinh cui cung khng oc co chinh xac cao hn chinh xac cua con s
it tin cy nht.
D tranh lam giam chinh xac cua kt qua do vic lam tron s o cac giai
oan trung gian, trong cac phep tinh chi oc oc phep lam tron o kt qua cui
cung.
-Phep cng va phep tru: chi giu lai o kt qua cui cung mt s thp phn
bng ung s thp phn cua s hang co s thp phn it nht.
1,2 10, ,1 0,0 Kt qua lam tron 0,1
11,1 1,2 3,11 Kt qua lam tron 3,1
-Phep nhn va chia: cn giu lai o kt qua cui cung mt s chu s co nghia
bng ung s chu s co nghia cua thua s co s chu s co nghia it nht.
3 3
10 . 3 , 1 10 . 3 , 1
1 , 3
02 , 0 . 120 , 1

{ {
1,3.10 3
3,1
1,120.0,02 kt qua lam tron 1,3.10-3
-Phep tinh logarit
VD: tinh logarit cua ,1.10-
Log -0,1 -,20 (co 3 chu s co nghia la 2, 0, tng tu
trong co 3 chu s co nghia.
VD: cho pH -lgH 11,1. Tinh H
H 10-11,1 ,0.10-12 lam tron H ,1.10-12 ( co 2 chu s co
nghia tng tu o gia tr pH co 2 chu s co nghia).
a. s= h! th=ng phan anh su sai lch giua gia tr trung binh voi gia tr thuc nn sai s
nay noi ln 9 kng cua quy trinh phn tich.
a. s= ngzu nhmn phan anh su sai lch giua tungg gia tr thi nghim ring r voi
gia tr trung binh nn noi ln 9 lup l8 #9 phn t+n cB. c+c kt 2B.) cua phep phn tich.
D lp lai va ung co th trung ngau va cung co th khac nhau.
D ung va lp lai cua phng phap phn tich
a. D lp lai va ung u thp; b. D ung cao, nhng lp lai thp; c. D lp
lai cao nhng ung thp; d. D ung cao va lp lai cung cao.
2.1..2. D ung, chinh xac, lp lai, nhay.
?9 kng phan anh su phu hop giua kt qua thuc nghim thu oc voi gia tr thuc
cua phep o.
Tham s anh gia ung la sai s tuyt i
va sai s tng i .
a. s= tuy!t =
phan anh su sai lch giua kt qua o x

i
hoc gia tr trung binh Z
va gia tr thuc .

Z
Z
Sai s tuyt i
khng cho ta thy muc gn nhau cua gia tr xac nh oc va

gia tr thuc tuc la khng cho ta thy oc ung cua phep phn tich. D bit oc
ung cua phep xac nh ngoi ta thong dung sai s tng i.
a. s= tKUng = phan anh lch tng i cua kt qua o voi gia tr thuc hoc gia
tr trung binh.
100
a
100
Z
a

?9 lup phan anh su phu hop giua cac kt qua thu oc trong cac thi nghim lp lai
trong cung mt iu kin thuc nghim ging nhau. Kt qua phn tich co th co lp cao
nhng khng ung va ngoc lai.
CAC DA LONG DAC TNG CHO DO PHN TAN.
D lch trung binh:
n
Z Z
,

Phng sai: la trung binh cng cua cac binh phng hiu giua cac gia tr ring le va
gia tr trung binh:
1
) (
2
2
n
Z Z
a
Trong o n la s ln thi nghim. Nu n gia tr nho, n20, n-1 oc gi la 6\c t3 ,-,

nu n ~20 thi co th bo qua s 1 bn canh n:
1
) (
2
2
n
Z Z
a
1
) (
2
2

n
Z
Cac ai long S
2
va o
2
u oc gi la phng sai la nhung ai long quan trng
c trng cho phn tan tinh sai s ngu nhin.
D lch chun hay sai s binh phng trung binh: bng cn bc hai cua phng sai.
1
) (
2

n
Z Z
a
1
) (
2

n
Z
D lch chun gia tr trung binh:

Phng sai cua gia tr trung binh bng phng sai chia cho s thi nghim:
n
a
a
Z
2
2
D lch cua gia tr trung binh:

n
a
a
Z

) 1 (
) (
1
2
n n
Z Z
a
n
Z
H s bin ng:
100 .
Z
a
P
2.1..3. Cac ham phn b va ung dung (ham Gauss, ham Student)
`hn 6= th3c ngh!%
Gia su kim tra th tich cua pipet dung tich 10 ml ta tin hanh cn th tich cua
pipet. Chung ta tin hanh 0 ln cn. Ghi cac kt qua vao mt bang thy oc quy lut
phn b cac kt qua thuc nghim o ta dung phng phap th. Trn truc hoanh ta biu
th gia tr th tich pipet (bng cach chia cac gia tr khi long noc cn oc cho khi
long ring cua noc), con trn truc tung ghi tn s tuc la s xut hin tung kt qua so
voi tng s ln xac nh th tich, ta s oc th biu th su phn b thuc nghim. Trn
bang 1 ghi tn xut phn b cac kt qua tinh oc tu cac kt qua thu oc cua 0 ln xac
nh dung tich pipet. Hinh la ong phn b thuc nghim.
Tn eu9t )hn bG !(! 6?t ru8 thA! nghi,7
?KLng phn 6= th3c ngh!% " 1< KLng phn 6= chu|n h.us #4)
!h"n b chun ha# $h"n b %au x& '%auss(
Thng thong nu sai s chua phep phn tich la sai s ngu nhin thi th biu
din su phn b cac kt qua thuc oc nh thi du trn y s co dang i xung.
Theo ly thuyt toan hc v xac xut thng k thi cac loai phn b quan trng va ph
bin nht la phn b chun hay phn b Gau x. Phn b chun hay phn b Gau x chi
ap dung voi cac thuc nghim co s ln thuc nghim v cung lon (n~0). Khi o cac ai
long ngu nhin trong hoa phn tich thong tun theo phn b nay. Ham phn b chun
s co dang nh sau:
2
) ( , 0
2
1

Z
e y
Trong o la gia tr thuc, x la gia tr thuc nghim, o la lch chun. y va o la nhung s
thuc, oc gi la tham s phn b, y lam ham s cua x chinh la tn s cua gia tr x hoc xac xut
cua x. Ham phn b co cuc ai o x va co im un x1 va x2 o.
`hn 6= chu|n h.y phn 6= h.u ZU #h.uss)
Theo phng trinh trn gia tr cuc ai cua y la
2
1
, gia tr o cang lon nu lch
chun o cang nho, hay noi cach khac lp lai cang cao nghia la s cac gia tr thu oc gn gia
tr thuc cang nhiu. Din tich cua hinh tao boi ong cong phn b va truc hoanh gm cac gia tr
x tu - n . Din tich gioi han trong khoang +2o la 0,; trong khoang + 3o bng 1. Vi
vy ngoi ta thong dung quy tc 3o phn bit ai long ngu nhin (sai s ngu nhin) voi
cac ai long h thng (sai s h thng) hoc phat hin sai s th.
78ng cB. KLng phn 6= chu|n ph0 thu9c 1<- 9 l!ch chu|n
D xu ly s liu cua thuc nghim co s ln thuc nghim n20 thong dung $h"n b
)tu*+nt '$h"n b t(.
2.1... Kim tra s liu thuc nghim
Sai s th: thong la nhung sai s lon, xut hin do su cu tha, nhm ln hoc su c
y gian ln, su truc trc bt ngo (do hong thit b, mt in, .). Sai s th co th lam hong
ca mt tp hop du liu nn cn phai loai bo troc khi tinh toan kt qua phn tich.
Loai bo s o thuc nghim sai s th bng chun Dison
Khi lam thi nghim, ta thu oc cac s liu, troc khi tinh toan ta cn kim tra cac
s liu thu oc xem no co mc sai s th hay sai s h thng khng loai cac s liu
o troc khi tinh toan. D loai bo cac s liu thuc nghim mc sai s th ta dung chun
Dison (chun ).
Dung chun hoc chun Di sn kim tra cac giu kin nghi ngo loai bo cac gia
tr mc sai s th khi s thi nghim n nho hn 10.
min max
1
Z Z
Z Z
n
n n

Trong o x
n
la gia tr ghi ngo, x
n 1
la gia tr ln cn gia tr x
n
va x
min
, x
max
tng ung
voi gia tr nho nht va lon nht.
Mun kim tra mt gia tr nao o, troc ht ta tinh gia tr
tn
(gi la thuc nghim)
theo cng thuc trn ri em so sanh voi gia tr
lt
(gi la ly thuyt trong bang Dison).
Nu gia tr
tn
~
lt
thi gia tr x
n
cn loai bo, con nu
tn

lt
thi gia tr thi nghim x
n
khng mc sai s th hay sai s h thng, co th dung oc.
Nu kim tra gia tr lon nht va nho nht ma khng phai loai gia tr nao thi khng
cn kim tra cac gia tr con lai. Ngoc lai nu mt gia tr nao b loai thi cn phai kim tra
gia tr tip theo k cn no.
Gia tr ung voi tin cy P va s ln o n
Th ,0* Nhung kt qua xac nh ham long Fe
2
O
3
trong mt loai mu la: 2,2;
2,11; 3,21; 2,1; 2,3; 2,32. Co nn loai bo gia tr nao khng.
Troc ht sp xp cac gia tr tng dn: 2,11; 2,1; ; 2,32; 2,3; 3,21, ta thy gia tr be
nht la 2,11 va gia tr lon nht lan 3,21. Kim tra gia tr 3,21.
, 0
11 , 2 21 , 3
3 , 2 21 , 3
tn
n
Tra bang thy ung voi n va P 0, thi
lt
0, vi
tn
ln hn
lt
nn cn bo
gia tr 3,11.
Sau o kim tra cac gia tr 2,3:
2 , 0
11 , 2 3 , 2
32 , 2 3 , 2
tn
n

lt
0,
ta thy cac
tn
u nho hn
lt
0, ung voi n, P 0, nn chung u la cac
gia tr ang tin cy.
Kim tra gia tr nho nht: 2,11.
3 , 0
11 , 2 3 , 2
1 , 2 11 , 2
tn
n

lt
0, khng b loai
Vy dy gia tr thuc nghim chi con gia tr: 2,11; 2,1; 2,2; 2,32; 2,3.
2.1... Biu din cac s o gian tip
Khoang tin cy va biu din s o theo chun Gauss (TK)
Khoang tin cy va biu din s o theo chun Student
Bin gioi tin cy la khoang trong o chua gia tr thuc .
D xu ly s liu cua thuc nghim co s ln thuc nghim n20 thong dung $h"n b
)tu*+nt '$h"n b t(.
n
a
Z
a
Z
t
Z
1
) (
2

n
Z Z
a
Gia tr t phu thuc vao s bc tu do k n - 1 va vao xac xut tin cy P. S thi nghim
cang nho, xac xut P cang lon thi gia tr t cang lon.
+i( tr 3ng &#i :C tin !I< P &2 @G bI! t4 do H S n X1
n
a t
Z

t
t Z
n
a t

- bin gioi tin cy
nh vy, gia tr thuc nm trong khoang x - c x c.
Voi xac sut tin cy nao o c oc biu th theo n v tuyt i nh x . nu biu th c
theo n v tng i () thi ta co:
n Z
a t
100
n Z
a t
Z

t
100
Y nghia cua cac con s trong bang Student: v mt xac xut ma noi, gia su P, lam
ln thi nghim (K3), thi cu 100 ngoi lam thi nghim thi co ngoi co gia tr t_3,1.
Dc im cua bang Student: voi cung xac xut P (trong cung mt ct) ta thy s thi
nghim cang nhiu thi gia tr t cang giam tuacs la gia tr thuc nghim cang gn voi gia trt huc.
Nhng voi cung s ln thi nghim (cung hang ngang) tin cy P cang lon thi t cung lon, bin
gioi tin cy c cang rng tuc la xac xut tim thy nhung gia tr gn voi gia tr thuc cang nhiu.
Bin gioi tin cy cang nho thi kt qua thi nghim Z cang gn gia tr thuc tuc la kt qua
cang chinh xac.
Vi du: tip tuc vi du o trn. Tinh bin gioi tin cy cua phep phn tich Fe
2
O
3
.
2 , 2
3 , 2 32 , 2 2 , 2 1 , 2 11 , 2 ...
2 1
+ + + +
+ + +
n
Z Z Z
Z
n
Bin gioi tin cy: k, P0,, t2,.
n
a t

11 , 0
0 , 0
1
) (
2

n
Z Z
a
1 , 0
11 , 0 , 2
n
a t
Kt qua:
1 . 0 2 , 2 t
/./. Ph"%ng )h() )hn t*!h tht t*!h
2.2.1. C so ly thuyt va nguyn tc cua phng phap
2.2.1.1. Cac khai nim c ban (nguyn tc, im cui, im tng ng, ong
cong chun ,.)
Nguyn tc: phng phap chun dua trn vic o chinh xac th tich dung dch
thuc thu (la dung dch chun) phan ung vua u voi dung dch phn tich. Tu th tich
va nng cua dung dch chun chung ta tinh ra ham long cht cn phn tich.
Dung dch thuc thu co nng xac nh gi la dung dch tiu chun. Dung dch
chun oc chun b bng mt trong 2 cach sau:
- cn chinh xac hoa cht oc chn pha dung dch chun, su o hoa
tan va pha thanh dung dch co th tich chinh xac.
- Cn chinh xac hoa cht oc chn sau o pha ch thanh dung dch.
Dung dch nay xac nh nng cua dung dch chun.
Hoa cht oc dung chun b dung dch chun u tin phai la hoa cht co
tinh khit cao, co cng thuc hoa hc xac nh va bn vung trong iu kin
bao quan binh thong. Hoa cht nay co phn tu long cang lon cang tt vi s
giam sai s tng i cua phep cn.
D tin hanh phn tich chun , ta lam nh sau: ly dung dch phn tich vao binh
non sach, thm cht chi th thich hop, ri thm tu tu dung dch chun tu buret vao dung
dch nh phn, qua trinh o gi la s3 chu|n 9.
Dim ma tai o dung dch tiu chun tac dung vua u voi dung dch phn tich gi la
% tKUng tKUng. D nhn bit im tng ng, ngoi ta dung cht gy ra su bin i
co th quan sat oc o sat im tng ng nh su thay i mau sc cua dung dch, su
xut hin kt tua, . Nhung cht nay gi la ch[t ch} th@.
Tai thoi im ma ta quan sat oc su bin i mau sc cua dung dch thi ngng
chun , thoi im o oc gi la % cu= ch|n 9.
Thng thong im cui chun khng trung voi im tng ng vi kho tim
oc cht chi th gy ra su thay i ung tai im tng ng. Vi vy phep chun
thong mc phai sai s.
Dong cong chun hay ong nh phn: D th biu din s phu thuc cua mt
ai long vt ly, hoa hc nao o lin quan n nng cac cht tham gia phan ung chun
vao th tich dung dch tiu chun a vao.
Tuy theo loai phan ung chun ma chon mi lin h thich hop.
Gia su co phan ung nh phn:
A B C
Trong o A la cht chun, B la cht cn chun va C la san phm.
Dong chun cua phan ung trn co dang nh sau:
a) cht chun A, b) cht phn tich B, d) san phan phan ung C
Thng thong d dang hn trong vic xac nh im tng ng, ngoi ta
thng biu din su phu thuc lg vao th tich cht chun thm vao.
2.2.1.2. u cu cho mt phan ung chun
Cac phan ung dung trong phn tich th tich phai thoa mn cac iu kin sau:
- cht nh phn (cn phn tich) phai phan ung hoan toan voi voi thuc thu theo mt
phan ung nht nh.
- phan ung xay ra nhanh va chn lc, nghia la thuc thu chi tac dung voi cht nh
phn chu khng tac dung voi cac cht khac co kaanx trong dung dch phn tich.
- phai co cht chi th thich hop nhn bit im tng ng.
`hn l-8 the- 6gn ch[t 1< cU ch phgn ]ng* Theo cach nay co bn cach chun :
a) Chun trung hoa (con gi la phng phap trung hoa):
Do la phep xac nh nng mt axit hay kim bng dung dch chun kim hay axit,
chi th cua phep chun nay la chi th pH, khoang pH i mau cua chi th nm trong
boc nhay pH cua phep chun , vi du Phenolphtalein, metyldacam.
b) Chun oxy hoa khu (con gi la phng phap oxy hoa khu): Phng phap nay
oc dua trn vic xac nh nng cac cht oxy hoa (hoc cht khu) bng cac cht khu
(hoc oxy hoa) chi th cua phep chun la cht chi th oxy hoa khu co khoang th i
mau nm gn hoc gn gn trong boc nhay th.
c) Chun kt tua (phng phap kt tua): San phm tao thanh la kt tua, song vn
nhn bit oc su i mau chi th nao o.
d) Chun tao phuc (phng phap tao phuc): San phm tao thanh phai la nhung
phuc cht u bn va tan trong noc. Dung dch chun cung la nhung cht tao phuc, chung
tao voi ion kim loai thanh phuc bn hn phuc cua chi th voi ion kim loai. Sau im
tng ng cung co su i mau r rt cua cht chi th.
2.2.1.3. Cht chi th:
2.2.1.. Dnh lut ng long, D chun, Ti phn chun F
?@nh lu\t KUng lKng* Cac cht phan ung voi nhau theo nhung ng long bng
nhau.
4
"
4
"
7
7
%
%
Gi V
A
, C
N
A
"
X
5
la th tich va nng ng long cua dung dch chun A.
Gi V
B
, C
N
A

4
X
5
la th tich va nng ng long cua cht nh phn B. Theo
nh lut ng long ta co:
4
X 4
"
X "
5 P 5 P
Dy la dang c ban cua nh lut ng long tinh toan trong phn tich th tich.
D
Ba(OH)2
M/2 , g
4
X 4
"
X "
5 P 5 P
22, . 0,0 20 . C
N (Ba(OH)2)
C
N (Ba(OH)2)

m
(Ba(OH)2)
C
N (Ba(OH)2)
. 0,2 . D
Ba(OH)2
?9 chu|n*
D chun T la s gam (hay miligam) cht tan trong 1mililit dung dch.
Cng thuc tinh :
P
.
T
a: s gam cht tan, V: th tich dung dch ml
D chun theo cht cn xac nh (cht nh phn): la s gam cht cn nh phn
(ion, phn tu, nguyn tu) phan ng ung voi 1 ml dung dch chun va oc ki hiu la
T
A/B
, trong o A la thuc thu, B la cht nh phn.
Vi du, T
AgNO3/Cl-
0,00 (g/ml) nghia la 0,00g cht nh phn Cl
-
tac dung vu u voi
1 ml dung dch chun AgNO
3
. Tu Vng Nghi tr. 2.
T} phWn chu|n 9 F*
Flong cht nh phn phan ung/long cht nh phn ban u
Trong qua trinh chun F s tng tu 0 n 1. Tai im tng ng F1.
2.2.2.. Phn loai cac phng phap chun theo trinh tu tin hanh chun
a) Chun truc tip: Cho dung dch chun tac dung truc tip voi dung dch nh
phn.
b) Chun gian tip: Cach nay dung nh long cht A khng th tin hanh
chun truc tip bng thuc thu nao o. Chuyn A vao mt hop cht thich hop chua it
nht mt nguyn t co th xac nh truc tip bng mt thuc thu nao y va cht chi th
thich hop.
Thuc t la vic xac nh A khng thng qua B ma phai co C (san phm cua A va B)
tac dung voi ri tu suy ngoc lai gian tip tinh ra A.
c) Chun ngoc: cach nay dung khi phan ung giua A va B xay ra chm hoc
khng tim oc cht chi th thich hop xac nh im tng ng.
Nguyn tc: them mt long chinh xac va d cht chun A vao dung dch cht nh
phn B, tao mi iu kin phan ung xay ra hoan toan. Sau o chun long thuc
thu A d bng dung dch chun thich hop. Dua vao th tich va nng cua cac dung
dch chun A va tim ham long B.
d) Chun thay th:
nguyn tc: cho cht cn nh phn B tac dung voi mt cht thch hop khac M,
giai phong ra :
B M MB
Sau o chun bng mt dung dch chun A thich hop. Dua vao th tich va nn
cua cht chun A, tinh oc ri suy ra B.
Cach nay dung khi khng co phan ung hoc cht chi th thich hop cho vic chun
truc tip B.
e) chun phn oan: chun ln lot cac cht , , ,. trong cung mt dung
dch bng mt hoc nhiu dung dch chun.
2.2.2.. Loc qui trinh phn tich bng phng phap th tich.
2.2.2.. Tinh toan kt qua trong phng phap phn tich th tich
Vic tinh kt qua phu thuc vao cach biu din nng va cach phn tich.
Nguyn tc chung: dua vao nh nghia nng , phng trinh phan ung chun
hoc nh lut v ng long ma tinh kt qua phn tich.
TrKLng hp chu|n 9 tr3c tp*
Cach tinh theo nng mol:
Dua vao th tich, nng dung dch chun va phng trinh phan ung tinh oc
long cht cn phn tich.
Vi du: khi chun 0,22 g Na
2
CO
3
tinh khit n CO
2
phai dung vua ht 22,3 ml
dung dch HCl. Tinh nng mol cua dung dch HCl o.
Ptpu: Na
2
CO
3
2HCl 2NaCl CO
2
H
2
O
S mol cua Na
2
CO
3
: 0,22/10 (mol)
S mol cua HCl: 2 x 0,22/10 (mol)
C
M(HCl)
2 x 0,22/(10.0.0223) 0,120 M
Cach tinh theo nng ng long: dua vao nh lut ng long 's ng
long mol cua dung dch chun bng s ng long mol cua cht phn tich phan
ung. D tinh khi long cht phan ung phai bit khi long mol ng long cua
cht o.
Tip tuc trang 30 , Tu Vng Nghi
/././. Ph"%ng )h() !huhn :C .!id B b.Q
2.2.2.1. C so va nguyn tc cua phng phap
Phng phap chun axit - baz dua trn phan ung trao i proton giua dung dch
chun va dung dch nh phn xac nh nng cua cac axit va baz. Cac dung dch
chun dung trong phng phap nay thong la cac dung dch axit manh hoc baz manh.
Trong qua trinh chun nng cua cac ion H
va OH
-
thay i, tuc la pH cua
dung dch nay thay i. D xac nh im tng ng ngoi ta thong dung nhung cht
ma mau sc cua chung thay i theo pH cua dung dch, gi la cht chi th axit - baz hoc
cht chi th pH.
Dong biu din su phu thuc cua pH trong qua trinh chun vao th tich dung
dch chun thm vao hoc long cht nh phn oc chun oc gi la ong
nh phn. Ngoi ta thong dua vao ong nh phn chn cht chi th thich hop nht.
Trong qua trinh chun , pH cua dung dch lun bin i mt cach tu tu nhng gn
n im tng ng (thong khi nh long thiu hoc thua +1 hay +0,1) co su
bin i t ngt cua pH (gi la boc nhay pH cua qua trinh nh long). pH o im
tng ng sec nm trong boc nhay pH nay.
2.2.2.2. Chi th acid baz
Cac cht chi th axit - baz la cac axit Hnd hoc baz ndOH huu c yu trong o
dang axit va baz lin hop co mau khac nhau. Vi vy mau cua chung phu thuc vao pH
cua dung dch. Trong noc cac cht chi th o phn ly nh sau:
Hnd H
nd
-
K
and
(a)
ndOH nd
OH
-
K
bnd
(b)
Su thay i mau cua cht chi th phu thuc vao pH cua dung dch oc giai thich
bng thuyt ion - mang mau: Khi pH thay i thi cac cn bng (a) hoc (b) s chuyn
dch v phia phai hoc phia trai, cht chi th s tn tai chu yu doi mt trong hai dang
lin hop, nn co mau cua dang nao tn tai chu yu trong dung dch.
Vi du: nu cht chi th la Hnd thi khi thm axit vao dung dch cua no thi cn bng
(a) s chuyn v phia trai nn dung dch co mau cua dang axit Hnd. Ngoc lai nu giam
axit cua dung dch (chng han thm kim vao) thi cn bng (a) s chuyn sang phia
phai nn dung dch co mau cua dang nd- (dang baz).
Khi pH cua dung dch chua cht chi th thay i thi cu truc cua phn tu trong o
co nhung nhom mang mau thay i dn n su thay i mau cua cht chi th.
Vi du: Phenolphtalein co th tn tai trong dung dch cac dang cu truc phn tu
sau y:
nh# @a. !`ng th3! Phgno;)ht.;gin (th.< C bng K)
Vi vy trong mi trong axit va trung tinh phenolphtalein tn tai chu yu doi
dang lacton khng mau, trong mi trong baz tn tai chu yu doi quinon mau hng,
nhng trong mi trong kim manh lai tn tai o dang khng mau.
Kh-gng %<u cB. ch[t ch} th@*
Mi cht chi th axit - baz thong co mt khoang pH i mau.
Ta hy xet cht chi th la axit huu c yu Hnd. Trong dung dch noc chua long
nho cua cht chi th o:
Hnd H
nd
-
K
and

[ ] [ ]
[ ] J_n,
_n, J
K
._n,
+
[ ]
[ ]
[ ]
_n,
J_n, K
J
._n,
[ ]
[ ]

_n,
J_n,
pK pJ
._n,
lg
Ti s
[ ]
[ ]
_n,
J_n,
thay i theo pH va chinh ti s nay quyt nh mau cua dung dch.
Mt thong chi phn bit oc su i mau khi nng cua dang axit chnh lch
voi nng dang baz khoang 10 ln, tuc la ti l
[ ]
[ ]
10
_n,
J_n,
hoc
[ ]
[ ] 10
1
_n,
J_n,
. Khi o ta
chi thy oc mau cua dang co nng lon hn.
1 t
._n,
pK pJ
Nh vy, khoang i mau ma mt ta nhn thy oc la 2 n v pH. Tuy nhin i
voi mt s cht chi th mt ta co th nhn oc su i mau nho hn 2 n v, nghia la khi
ti s nng cua cac dang nho hn 10 ln. Di voi cht chi th loai ndOH, ta cung lp
lun tng tu xac nh khoang pH i mau. Trong bang sau y la mt s cht chi th
axit - baz quan trng nht.
dCt @G !h9t !hn th .e*tXb.Q% ru.n trkng
Tn thng dung Khoang i mau pTpK
a
Mau dang acid - baz
Thimol xanh 1,2 2, 1, Do - vang
Metyl vang 2, ,0 3, Do - da cam
Metyl da cam 3,1 , 3, Do - da cam
Bromcresol xanh 3, , , Vang - xanh
Metyl o ,2 ,3 ,00 Do - vang
Bromcresol tia ,2 , ,12 Vang o tia
Bromthimol xanh ,2 , ,10 Vang - xanh
Phenol o , , ,1 Vang o
Cresol tia , ,2 ,0 Vang tia
Phenolphtalein ,3 10 ,1 Khng mau hng
Thimolphtalein ,3 10, ,0 Khng mau xanh
Alizann GG 10 -12 11,00 Khng mau xanh
Di voi loai cht thi th co mau tuc la chi mt trong hai dang axit - baz lin hop co
mau, chng han cht chi th loai Hnd ma dang Hnd khng mau thi mau cua dung dch s
do nng dang co mau nd- quyt nh. Nu C la gia tr ma nng nd
-
cn at toi
ta nhn ra mau cua no va Co la nng ban u cua cht chi th thi pH cua dung dch tai
o mau cua nd bt u xut hin la:
5
5 5
pK pJ
._n,

0
lg
Nh vy, pH lam i mau phu thuc vao nng cht chi th. Vi du, trong dung
dch phenolphtalein bo hoa, mau hng xut hin khi pH con trong dung dch long
hn 10 ln thi pH moi xut hin mau.
Ngoai khoang i mau cua cht chi th, ngoi ta con dung khai nim chi s pT cB.
ch[t ch} th@ .Zt R 6.>U ch} pJ %< t8 ch[t ch} th@ %<u r~ nh[t. Ta thong thy
gia tr pT trung voi gia tr pK
and
cua cht chi th.
Sai s chi th: thong gp khi gia tr pT cua cht chi th khng trung voi im tng
ng. Sai s chi th oc tinh theo cng thuc sau:
100
?
? h
a
G la gia tr gn ung
D gia tr ung
Khi pT pH
TD
(chun kt thuc troc im tng ng) thi:
100

,.u 6.n ch.t lu-ng
chu.n chu. ch.t lu-ng
a
Khi pT pH
TD
(chun kt thuc sau im tng ng) thi:
100

+
,- chu.n ,e c.n thu thu-c lu-ng
,u thu thu-c lu-ng
a
2.2.2.3. Cac phng phap chun acid baz
Cht chun thong dung trong chun acid baz la cac acid manh va baz manh
(HCl, NaOH, KOH, H
2
SO
).
2.2.2.3.1. Chun acid manh - baz manh
Gia su chun V
0
ml axit manh HA nng C
o
(mol/l) bng dung dch chun baz
manh NaOH hoc KOH nng C (mol/1).
HA H
A
-
H
2
O H
OH
-
[ ] [ ] [ ]
I J
IJ " J
2
+
+
Phng trinh phan ung chun la:
HA NaOH NaA H
2
O
Dang ion:
H
OH
-
H
2
O
Ti phn chun
0 0

P 5
5P
,.u 6.n .c, %-l s-
1.- the% ,. 6.> %-l s-
F
Phng trinh bao toan proton cua dung dch trong qua trinh chun :
[ ] [ ] [ ] [ ]
X.IJ I J
IJ IJ " J
+
+
2
[ ] [ ]
P P
5P
IJ
P P
P 5
J
+
+
+
+
0 0
0 0
[ ] [ ] ( ) 1
0 0
0

+
+
F
P 5
P P
J IJ
Phng trinh trn la phng trinh tng quat cua ong nh phn, no cho ta bit
mi lin h giua pH cua dung dch va phn axit oc chun . Nu bit oc gia tr
cua V, ta bit oc F va dua vao phng trinh trn ta tinh oc H
, tuc la pH cua dung

dch.
Khi moi chun con tng i xa im tng ng, trong dung dch con nhiu
H
, nn H
~~ OH
-
nn suy ra:
(*)
Phng trinh trn cho ta thy nng H
bng nng axit cha oc chun

b pha long bng V ml dung dch chun NaOH oc thm vao. Troc im tng
ng ( C.VC
0
.V
0
):

[ ]
0
0 0
. .
lg lg
P P
P 5 P 5
J pJ
+

+
(*)
[ ]
0
0 0
. .
P P
P 5 P 5
J
+
+
[ ]
0
0 0
.
) 1 (
P P
P 5
F J
+

+
Tuy nhin, iu nay chi ung khi tng i xa im tng ng. Cang gn n
im tng ng ta phai k n su phn ly cua noc. Tai im tng ng khi F 1,
ta co:
,
Tai im tng ng ( C.VC
0
.V
0
): khi nay toan b long axit b trung hoa boi
kim. do o dung dch trung tinh, pH.
Sau va xa im tng ng vi d tng i nhiu NaOH nn OH
-
~~ H
. Sau
im tng ng ( C.V~C
0
.V
0
):
(**)
[ ]
0
0 0
.
) 1 (
P P
P 5
F IJ
+

0
0 0
. .
lg 1 1
P P
P 5 P 5
pIJ pJ
+
+
(**)
Sat troc va sau im tng ng H
- OH
-
nn phai giai phng trinh tinh
pH. Cn chu y rng, co th coi CV CoVo, tuc la:
(***)
Nhn xet v ong nh phn axit manh bng baz manh:
- Dim tng ng trung voi im trung hoa pH.
- Troc va sau im tng ng khi F nho hn 0, va lon hn 1,01 thi pH cua
dung dch bin i rt it. Trai lai o vung gn im tng ng pH thay i rt nhiu tao
nn boc nhay pH o sat im tng ng.
- Doan pH ung voi thoi im con 0,1 long axit cha oc chun va 0,1 long
kim d so voi axit, tuc la khoang pH ung voi F 0, va 1,001 thong oc quy oc
la boc nhay cua ong nh phn.
- Dua vao boc nhay cua ong nh phn ta co th d dang chn cht chi th. Trong
trong hop nay ta chn bt ky cht chi th nao co pT nm trong boc nhay.
- Nng axit cang lon thi boc nhay cang dai.
Tnh pJ cB. 6Kfc nhgy.
Khi chun thiu 0,1 tuc la:
Gia su C va C
o
gn im tng ng nn V gn V
o
, ngoai ra co th bo qua OH
-
canh H
, nn phng trinh trn oc n gian thanh:

Khi chun thua 0,1 tuc la:
Vi sau im tng ng nn ta bo qua H
canh OH
-
va co th coi V V
o
nn:
Boc nhay bng hiu s 2 gia tr pH trn ApH:
0,1 HCl 0,1 NaOH ( )
0,001 HCl 0,001 NaOH ( )
Vi du: V ong nh phn khi chun 100ml dung dch HCl 0,1M bng dung
dch NaOH 0,1M.
Ap dung cng thuc (*), (**) kt hop voi (***) ta tinh oc pH khi cho nhung th
tich NaOH khac nhau vao dung dch HCl chun HCl. Cac kt qua oc tp hop
trong bang sau:
5hu|n ?9 4.>- S8nh 4Ong "Zt S8nh*
Gia su chun V
0
ml baz manh NaOH nng C
o
(mol/l) bng dung dch chun
acid manh HA nng C (mol/1).
- Troc im tng ng ( C.VC
0
.V
0
)
[ ]
0
0 0
. .
lg lg
P P
P 5 P 5
IJ pIJ
+

~ pH 1 pOH
- Tai im tng ng ( C.VC
0
.V
0
): khi nay toan b long kim b trung hoa
boi axit. Do o dung dch trung tinh, pH.
- Sau im tng ng ( C.V~C
0
.V
0
):

0
0 0
. .
lg 1 1
P P
P 5 P 5
pJ pIJ
+
+
~ pH 1 pOH
2.2.2.3.2. Chun n acid yu bng baz manh
Gia su chun V
0
ml axit yu HA voi hng s acid K
a
, nng C
o
(mol/l) bng
dung dch chun baz manh NaOH hoc KOH nng C (mol/1).
Ptpu: HA NaOH NaA H
2
O
HA OH
-
A
-
H
2
O
Phng trinh ong nh phn:
[ ] [ ] ( )
[ ]
[ ]
.
K J
J
P 5
P P
J IJ F
+
+

+
+
+
0 0
0
1
- khi cha thm NaOH, trong dung dch chi chua acid yu HA, pH cua dung dch
tinh theo cng thuc:
[ ]
[ ]
+
+
+
J K
5 K
J
.
. 0
[ ]
0
5 K J
.

+

0
lg
2
1
2
1
5 pK pJ
.

X 0F1: Troc im tng ng (C.VC
0
.V
0
), long NaOH cho vao khng u
trung hoa ht long acid. Trong dung dch luc nay chua HA cha b trung hoa va baz lin
hop cua no la A
-
, co nghia la dung dch luc nay la mt h m HA/ A
-
, pH cua dung dch
oc tinh theo cng thuc:
6
.
.
5
5
pK pJ lg
Voi
C
a
: la nng cua axit yu cha b trung hoa
C
b
: la nng cua bazo lin hop cua axit yu oc tao thanh trong qua
trinh chun .
- F1: im tng ng (C.VC
0
.V
0
), long NaOH vua u trung hoa acid yu,
trong dung dch chi chua baz yu A
-
, pH cua dung dch luc nay oc tinh theo cng thuc:
[ ]
0
0
2
5 5
5 5
K K J
. I J
+

+
0
0
lg 1
5 5
5 5
pK pJ
.
+
+
- F~1: Sau im tng ng (C.V~C
0
.V
0
), khi thm NaOH d, trong dung dch
chua NaOH d va baz yu A
-
. Vi A
-
la baz yu bn canh NaOH la mt baz manh nn pH
cua dung dch oc tinh theo NaOH:
0
0 0
. .
lg 1
P P
P 5 P 5
pJ
+
+
Nhn xet v ong cong chun trong trong hop chun axit yu bng baz
manh:
- Cung ging nh chun n axit manh bng baz manh, troc va sau im tng
ng khi chun n axit yu bng baz manh pH it bin i theo F nhng o sat im
tng ng pH tng t ngt theo F tao nn boc nhay cua ong nh phn. Nu cung
qui oc boc nhay la pH ung voi su chun thua va thiu 0,1 long axit thi trong
trong hop nay boc nhay ngn hn trong hop chun axit manh bng baz manh.
- Khac voi trong hop chun axit manh khi chun axit yu pH tai im tng
ng khng bng ,0 ma lon hn vi san phm cua pa phan ung chun la baz yu
CH
3
COONa.
- Boc nhay cua ong nh phn phu thuc vao cong axit. Axit cang yu thi
boc nhay pH o vung im tng ng cang ngn. Ta hy gia su chun cac dung
dch axit HA nng 0,1 M bng dung dch chun NaOH 01M. Cac axit o co pha ln
lot la 3, , , va . Trong trong hop nay ta s tinh pH tai im tng ng va boc
nhay la gia tr ApH khi chun thiu va thua 0,2. Ta co bang sau:
ua cac kt qua trn ta thy, cac dung dch axit cung nng nhng co pK
a
khac
nhau thi voi axit cang yu, tuc co pKa cang lon thi pH tai im tng ng cang lon
hn nhiu va boc nhay pa tai im ng ng cang ngn. Khi pKa bng thi thuc
t khng co boc nhay. Di voi axit co pK
a
bng boc nhay pH cha at oc 0, n
v pH; nn kho chn oc cht chi th co th phn bit oc su i mau bng mt
thong. Di voi axit co pK
a
bng hoc thi khng th chun oc vi khng th
chn oc cht chi th.
- Boc nhay cua ong nh phn con phu thuc vao nng cua axit cn chun
va nng cua dung dch chun baz manh.
Ta hy tinh noc nhay ong nh phn khi chun cac dung dch CH
3
COOH pK
a
, co cac nng la 1,0; 0,1; 0,01; 0,001M bng cac dung dch chun NaOH cung
nng . Trong trong hop nay gia su boc nhay ung voi F - 1 + 0,002; tuc la chun
thiu va thua 0,2 long axit cn chun . Sau khi giai phng trinh (a), ta oc cac
kt qua sau:
ua cac vi du trn ta thy boc nhay cang ngn nu nng axit cang nho. Cac
dung dch nng nho hn 0,001M gn nh khng co boc nhay, nn nu chun s
mc sai s chi th rt lon hoc khng th chn oc cht chi th.
2.2.2.3.3. Chun n baz yu bng acid manh
Gia su chun V
0
ml baz yu B voi hng s baz K
b
, nng C
o
(mol/l) bng dung
dch chun acid manh HCl nng C (mol/1).
Tng tu nh trong hop chun acid yu bng baz manh.
- F0:
6
5
6
K IJ .
1
1
]
1
6 6
5 K pIJ pJ lg
2
1
lg
2
1
1 1 + +
- 0F1, C.VC
0
.V
0
: dung dch m
6
.
.
5
5
pK pJ lg
6 .
pK pK 1
Voi
C
a
, C
b
la nng cua cp axit va baz lin hop.
- F1: im tng ng (C.VC
0
.V
0
): pH oc xac nh boi acid
lin hop cua baz yu:
. .
p5 pK J pJ
2
1
2
1
lg +
1
]
1
+

Voi K
a
la hng s cn bng cua axit lin hop cua bazo yu
Va C
a
la nng cua axit lin hop cua bazo yu o
- F~1: Sau im tng ng ( C.V~C
0
.V
0
): pH cua dung dch do acid manh quyt
nh:
0
0 0
. .
lg
P P
P 5 P 5
pJ
+

Nhn xet: ging voi trong hop trn
2.2.2.3.. Chun a acid
Ta hy thit lp ong inh phn chun dung dch a axit H
2
A voi hng s cn
bng K
a1
, K
a2
nng la C
o
(mol/l); bng dung dch chun ba manh NaOH nng C
(mol/l).
D thy r hai boc nhay trn ong nh phn thi K
a1
va K
a2
phai khac nhau it nht
10
ln.
Su chun nay oc tin hanh theo 2 nc:
H
2
A OH
-
HA
-
H
2
O
HA
-
OH
-
A
2-
H
2
O
Khi chun theo cac nc thu nht, tuc la tin hanh chun theo phan ung (a) thi
tai im tng ng thu nht, ta co F 1. Khi chun theo nc thu 2, tuc la tip theo
phan ung (b), tai im tng ng thu 2, ta co F 2.
[ ] ( ) " J pK pJ
. 2 1
lg
2
1

[ ]
[ ] " J
J"
pK pJ
.
2
1
lg

+
) (
2
1
2 1 . .
pK pK pJ +
[ ]
[ ]
+
J"
"
pK pJ
.
2
2
lg
[ ] ( )

2
2
lg
2
1
" pK pIJ
6
[ ] ( )

2
2
lg
2
1
2
" pK pK pIJ
. I J
[ ] ( )
+ +
2
2
lg 1
2
1
" pK pJ
.
Chi th bc 1: metyl o hoc metyl da cam
Chi th bc 2: phenolphtalein
2.2.2.3.. Chun a baz
2.2.2.3.. Chun hn hop acid (TK)
2.2.2.3.. Chun hn hop baz (TK)
2.2... Vi du nh long bng phng phap chun acid baz
2.2...1. ac nh nng HCl, NaOH theo cht gc
Nhung dung dch chun thong dung trong phng phap acid baz:
- dung dch acid HCl, H
2
SO
nh long baz
- dung dch NaOH, KOH nh long acid.
Nhng ta khng th pha cac dung dch nay bng cach cn chinh xac vi chung
thong khng tht tinh khit hoc thanh phn khng tht n nh.
Vi du: H
2
SO
d hut noc, NaOH d hut noc va chua Na

2
CO
3
do hp thu khi CO
2
trong khng khi. Nn troc khi dung nhung cht nay trong vai tro cht chun phai xac
nh nng ng long cua chung bng nhung dung dch gc oc iu ch tu cht
gc.
Cht gc la nhung cht:
- co tinh khit cao (tkpt)
- co thanh phn ung cng thuc hoa hc
- bn o ngoai khng khi va trong dung dch
Cac cht gc thong dung:
- HCl ng phi, ocid oxalic xac nh nng ng long cua
dung dch kim.
- Natri borat, natri cacbonat xac nh nng ng long cua
acid.
Khi un nong dd HCl c, u tin HCl bay ra cung voi 1 lg hi noc.Dn khi nng
dd con 20,2 thi HCl va H2O tao thanh hh ng phi,si o 110*c". Hn hop ng phi
la hn hop ng si. Tai im ng phi, pha long va pha hi co cung mt thanh phn cac
cu tu, do o nu un si HHDP thi pha hi sau khi ngng tu s co thanh phn ging nh
pha long ban u, co nghia la HHDP khng th tach thanh cac cu tu ring bit bng
phng phap chng ct ( la hn hop cht long khi si khng thay i thanh phn va nhit
si. Hay d hiu hn la hn hop ma khi si thi cht tan va dung mi u si.). O y
tai nng 20.2 thi khi si , HCl s bc hi cung hi noc, do o ko th tach HCl hoan
toan khoi dd.
HCl, NaOH la acid va baz manh oc su dung lam thuc thu (dung dch chun)
trong chun aicd baz.
D pha dung dch NaOH cn mt long cht rn NaOH co khi long chinh xac trn
cn k thut va pha trong mt th tich xac nh.
Vi NaOH rn d hut CO
2
va hi noc cua khng khi nn thong co ln mui
Na
2
CO
3
va hi noc nn khng th la cht chun gc. D xac nh chinh xac nng cua
NaOH troc khi dung lam dung dch chun trong chun cn phai chun bng dung
dch acid oxalic voi cht chi th phenol phtalein.
Dung dch acid oxalic oc iu ch tu cht gc H
2
C
2
O
.2H
2
O (M12,0).
Vi du: chun dung dch NaOH co nng khoang 0,1M bng dung dch aicd
oxalic 0,0 M.
- pha dung dch co nng khoang 0,1M, ta cn trn cn k thut khoang
,1 g NaOH loai tinh khit phn tich va pha thanh 1l dung dch bng noc
ct. Dung dch moi pha ung trong binh polyetylen.
- Acid oxalic oc iu ch bng cach cn ,3033 g tinh th H
2
C
2
O
.2H
2
O
(M12,0) loai tinh khit phn tich, chuyn vao binh nh muc sach 1
lit, hoa tan bng noc ri nh muc toi vach muc. Dung dch moi pha ung
trong binh polyetylen hoc binh thuy tinh nut nham.
Dung pipet ly 2 ml dung dch H
2
C
2
O
cho vao binh non 20 ml rua sach

va trang 3 ln bng noc ct, thm vao git phenol phtalein. Tu buret ung dung dch
NaOH cn xac nh nng , nho tu tu dung dch NaOH vao binh non, vua nho vua lc
cho n khi dung dch chuyn sang mau hng nhtk bn trong vai giy. Ghi lai gia tr th
tich acid oxalic dung. Tin hanh lam 3 ln va ly kt qua trung binh.
Ptc: H
2
C
2
O
NaOH Na
2
C
2
O
2H
2
O
2 .
.
2 2 2 2
X.IJ
I 5 J I 5 J
X.IJ
P
5 P
5
HCl oc iu ch bng cach pha long dung dch HCl m c 3, d1,1 g/ml.
Tng tu HCl m c 3, d1,1 g/ml la dung dch cua khi HCl trong noc nn d
bay hi, cung khng th la cht chun gc.
Cht chun gc trong vic chun dung dch HCl la Na
2
B
.H
2
O voi cht chi th
metyl cam hoc metyl o. Dung dch chun Na
2
B
oc iu ch bng cach hoa tan

khi long xac nh cht rn trong noc ct.
B
2-
H
2
O

2H
2
BO
3
-
2H
3
BO
3
2H
2
BO
3
-
2H
2H
3
BO
3
B
2-
H
2
O 2H
H
3
BO
3
2.2...2. Dnh long NaOH (TK)
2.2...3. Dnh long HCl (TK)
2.2.... Dnh long CH
3
COOH (TK)
2.2.... Dnh long NH
3
(TK)
2.2.... Dnh long NH
Cl (TK)
2.2.... Dnh long hn hop mui Na
2
CO
3
va NaHCO
3
Hn hop Na
2
CO
3
va NaHCO
3
chun bng dung dch chun HCl. Phan ung chun
xay ra nh sau:
Na
2
CO
3
HCl NaHCO
3
NaCl (1) chi th phenol phtalein
NaHCO
3
HCl NaCl H
2
O

CO
2
(2) chi th mety da cam
Khi dung chi th phenol phtalein luc chuyn mau ung voi phng trinh phan ung (1).
Sau o tip tuc chun voi metyl da cam, khi cht chi i mau la luc phng trinh (2)
xay ra hoan toan.
2.2.... Dnh long hn hop acid (HCl va H
3
PO
) (TK)
2.2.... Dnh long hn hop baz (NaOH va Na
2
CO
3
)
Phan ung chun :
Cht chi th phenol phtalein:
NaOH HCl NaCl H
2
O
Na
2
CO
3
HCl NaHCO
3
NaCl
Cht chi th metyl da cam:
NaHCO
3
HCl NaCl H
2
O

CO
2
/./.3. Ph"%ng )h() !huhn :C oei ho( 6ha
2.2.3.1. C so va nguyn tc cua phng phap
Phng phap chun oxi hoa khu dua trn phan ung chun la phan ung trao
i electron giua dung dch chun chua cht oxi hoa (hoc khu) voi dung dch phn tich
chua cht khu (hoc cht oxi hoa). D nhn ra im tng ng cua phan ung chun ,
ngoi ta dung cht chi th.
2.2.3.2. Cht chi th th in cuc
Trong chun oxi hoa khu mt s trong hop co th nhn ra im cui cua phan
ung chun bng su thay i mau cua dung dch khi d mt git dung dch chun. Vi
du, khi chun dung dch cua cht khu khng mau bng dung dch chun pemanganat,
thi mt git dung dch chun d ra cung u lam dung dch co mau hng.
Mt trong hop khac la mt trong hai dang oxi hoa hoc khu tao cht mau voi mt
cht khac, nh iot tao mau xanh voi h tinh bt, nn dung h tinh bt lam cht chi th cho
phan ung chun iot hoc chun dung dch cht khu bng dung dch chun iot.
Trong trong hop nay h tinh bt khng tham gia vao phan ung oxi hoa khu.
Trong ai a s cac trong hop cht chi th trong chun oxi hoa khu la nhung
cht oxi hoa hoc khu ma dang oxi hoa hoc khu cua no co mau khac nhau, vi vy mau
cua cht chi th phu thuc vao th oxi hoa khu cua dung dch. Mi cht chi th oxi hoa
khu cung co mt khoan i mau.
Giua dang oxi hoa va dang khu cua cht chi th oxi hoa khu tn tai cn bng trao i
electron nh sau:
nd
Ox
ne nd
ed
Pt Nerst i voi h nay:
[ ]
[ ]
,
IZ
_n,
_n,
_n,
n
E E
e
0
lg
0 , 0
+
Mt ta co th phn bit oc mau cua mt dang nao la tuy thuc vao ti s nng
dang oxy hoa va dang khu trong dung dch. Thong thi mt ngoi co th nhn oc mau
cua dang oxy hoa hay dang khu khi ti s o hn kem nhau 10 ln, nghia la:
Khi
[ ]
[ ]
10
e

,
IZ
_n,
_n,
dung dch co mau dang nd
Ox
, ung voi dung dch co
n
E E
_n,
0 , 0
0
+
,
Khi
[ ]
[ ]
10
e

,
IZ
_n,
_n,
dung dch co mau dang nd
ed
, ung voi dung dch co
n
E E
_n,
0 , 0
0

,
Nh vy, mau cua cht chi th trong dung dch s bin i tu mau cua dang nd
Ox
sang dang nd
ed
( mt nhn thy oc) ung voi th cua nm trong khoang:
n
E E
n
E
_n, _n,
0 , 0 0 , 0
0 0
+
va khoang gioi han nay gi la khoang i mau cua cht chi th oxy hoa khu .
Vy khoang i mau cua cht chi th oxy hoa khu la khoang gia tr in th ma
trong khoang o khi cua dung dch thay i thi mau cua cht chi th oxy hoa khu thay
i (mt ngoi nhn thy oc).
Lu y: do 0,0/n la qua nho, trong thuc t khoang i mau gn trung voi gia tr th
0
cua cht chi th oxy hoa khu nn ngoi ta chi quan tm n gia tr th
0
cua cht chi
th va dung lam 'th i mau.
Mt s cht chi th oxy hoa khu hay dung:
Chi th Mau dang oxi hoa Mau dang khu
nd
0
, V
Diphenylamin anh tim Khng mau 0,
Diphenylbenzidin Mau tim Khng mau 0,
Acid diphenylazosulphonic Do tim Khng mau 0,
Acid phenylantranilic Do tim Khng mau 1,0
Pheroin anh nhat Do 1,0
Axio, o-diphenylamindicacbonic anh tim Khng mau 1,2
2.2.3.3. Phng trinh ong nh phn va sai s chi tr trong chun oxi hoa
khu:
Trong phng phap chun oxi hoa khu, th cua dung dch s thay i theo th tich
cua dung dch chun thm vao dung dch cn chun . Dong biu din th cua dung
dch () theo th tich cua dung dch (V) chun thm vao la ong cong chun .
Mun v ong cong chun ta tinh th cua dung dch (theo phng trinh Nerst)
sau mi ln thm thuc thu.
Vi du: v ong cong chun V
0
ml dung dch Fe
2
, nng ng long C
N
0
bng dung dch chun Ce
nng ng long C
N
.
Pt chun :
Ce
Fe
2
Ce
3
Fe
3
Trong o th tiu chun cua h nh sau:
[ ]
[ ]
[ ]
[ ]
+
+
+
+
+
+
+ +
3
0
/
lg 0 , 0 , 1
lg 0 , 0
3
5e
5e
E
5e
5e
E E
5e 5e
,
[ ]
[ ]
[ ]
[ ]
+
+
+
+
+
+
+ +
2
3
2
3
0
/
lg 0 , 0 , 0
lg 0 , 0
2 3
Fe
Fe
E
Fe
Fe
E E
Fe Fe
- Khi C
N
.V
0
X
5
. V
0
, F1, troc im tng ng. Nng cua Fe
2
va Fe
3
d
tinh hn nn tinh in th dung dch theo Fe:
[ ]
[ ]
+
+
+
+ +
2
3
0
/
lg 0 , 0
2 3
Fe
Fe
E E
Fe Fe
Trong o:
[ ]
0
3
P P
P 5
Fe
X
+
+
,
0
0
P 5
P 5
F
X
X
[ ] [ ]
P P
P 5 P 5
P P
P 5
P P
P 5
Fe 5 Fe
X X X X
Fe
+
+

+ +
+
0
0
0 0
0
0
3 2
2
[ ]
[ ] P 5 P 5
P 5
P 5 P 5
P P
P P
P 5
Fe
Fe
X X
X
X X
X
+
+
0
0
0
0
0
2
3
P 5 P 5
P 5
E E
X X
X
Fe Fe
+
+ +
0
0
0
/
lg 0 , 0
2 3
Chia tu va mu biu thuc doi lg cho
0
0
P 5
X
, ta co:
F
F
E E
Fe Fe
+
+ +
1
lg 0 , 0
0
/
2 3
- Khi C
N
.V
0
X
5
. V
0
- im tng ng, khi o
Ce
Fe
2
Ce
3
Fe
3
[ ]
[ ]
+
+
+
+ +
3
0
/
lg 0 , 0
3
5e
5e
E E
5e 5e
t
,

[ ]
[ ]
+
+
+
+ +
2
3
0
/
lg 0 , 0
2 3
Fe
Fe
E E
Fe Fe
t
D tinh
t
ta cng hai phng trinh trn, khi o ta co:
[ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ] [ ]
+ +
+ +
+
+
+
+
+ +
+ + +
+ + + +
+ + + +
2 3
3
0
/
0
/
2
3
3
0
/
0
/
lg 0 , 0 2
lg 0 , 0 lg 0 , 0 2
3 2 3
3 2 3
Fe 5e
Fe 5e
E E E
Fe
Fe
5e
5e
E E E
5e 5e Fe Fe
t
5e 5e Fe Fe
t
2
0
/
0
/
3 2 3 + + + +
+
5e 5e Fe Fe
t
E E
E
- Khi C
N
.V ~
0
X
5
. V
0
, F~1 sau im tng ng, khi o tinh nng cua Ce

Ce
3
d dang hn nn:
[ ]
[ ]
+
+
+
+ +
3
0
/
lg 0 , 0
3
5e
5e
E E
5e 5e
[ ]
P P
P P 5
P P
P 5 P 5
P P
P 5 P 5
5e
t X t X X X X
+
+
0 0 0
0
0
) (
[ ]
P P
P 5
P P
P 5
5e
X t X
+
+
0
0
0
0
3
[ ]
[ ]
0
0
0
0
0
0
3
) ( ) (
P 5
P P 5
P 5
P P
P P
P P 5
5e
5e
X
t X
X
t X

+
+
[ ]
[ ]
0
0
0
/
3
0
/
) (
lg 0 , 0
lg 0 , 0
3
3
P 5
P P 5
E E
5e
5e
E E
X
t X
5e 5e
5e 5e
+
+
+ +
+ +
+
+

0
0
0
/
) (
lg 0 , 0
3
P 5
P P 5
E E
X
t X
5e 5e

+
+ +
) 1 lg( 0 , 0
0
/
3
+
+ +
F E E
5e 5e
Vi du: 1 va 2 trang 11-1, Trn Tu Hiu
Nhn xet:
- Dong chun trong phng phap oxi hoa khu cung co boc nhay
th o im tng ng ging nh ong chun trong phng
phap trung hoa co boc nhay pH.
- Boc nhay th cung phu thuc vao nng cua cac dung dch, th
cua cac cp oxi hoa khu. Nng cac cht tham gia phan ung cang
lon va th oxi hoa khu tiu chun cua cac cp oxi hoa khu khac nhau
cang nhiu thi boc nhay th cang dai.
- Tai vun xung quanh im F0, th bin thin rt it, ta co th dung
lam dung dch m th.
- Cach chn cht chi th: chn cht chi th co khong th i mau nm
trong khoang boc nhay th.
D lua chn cht chi th hop li thi cn phai tim sai s chi th.
Sai s chi th: oc tinh theo cng thuc sau:
1
0 0
0 0

5
F
P 5
P 5 5P
a
Trong o, F
C
la F tai im cui, tuc im ta kt thuc chun .
Nguyn tc chung tinh sai s chi th trong chun oxi hoa khu:
Tinh th tai im tng ng
t
. Tu o so sanh th o im cui
c
voi
t
xem kt
thuc chun troc hay sau im tng ng chn phng trinh tinh F. Sau o tinh
S.
Vi du: vi du 1, 2 trang 20, Tu Vng Nghi
2.2.3.. Cac phng phap chun oxi hoa khu thong dung
2.2.3..1. Phng phap permanganat (trang 10, Trn Tu Hiu)
La phng phap nh long dua vao kha nng oxi hoa cua permanganate o ca trong
mi trong acid, trung tinh, kim.
Trong mi trong acid manh MnO
2-
b khu n Mn
2
:
MnO
-
e H
Mn
2
H
2
O
(mau hng) (khng mau)
P E
Sn SnI
1 , 0
0
/
2 2

+
Trong mi trong aicd yu, trung tinh hay kim, MnO
2
2-
b khu n MnO
2
.
MnO
-
3e H
MnO
2
2H
2
O (acid yu)
(mau hng) mau nu
P E
SnI SnI
, 1
0
/
2
2
MnO
-
3e 2H
2
O MnO
2
OH
-
(trung tinh hay kim)
P E
SnI I J SnI
, 0
0
/ 2
2 2
2
Co th giai thich su khac bit v kha nng oxi hoa khac nhau cua MnO
2
2-
trong mi
trong acid va mi trong kim bng phan ung sau:
MnO
2
2e H
Mn
2
2H
2
O (*)
Trong mi trong acid cn bng (*) s dch chuyn v phia phai tao ra Mn
2
.
Nh vy co th coi rng trong mi trong acid MnO
2-
troc tin b khu thanh MnO
2
sau o do nng ion H
trong dung dch cao nn lp tuc MnO

2
b khu tip xung Mn
2
.
Trong mi trong trung tinh hay kim thi MnO
2
2-
b khu toi MnO
2
va khng b khu tip
nua vi trong mi trong nay cn bng (*) chuyn dch sang trai, tao thanh MnO
2
.
Nh vy kha nng oxi hoa cua MnO
2
2-
trong mi trong acid lon hn nhiu so voi
mi trong kim. Hn nua trong mi trong aicd, san phm la Mn
2
khng mau, nn
chinh KMnO
cung la chi th cho qua trinh chun , vi sau im tng ng 1 git

dung dch KMnO
d cung u lam cho dung dch chuyn tu khng mau sang mau hng.
Kt tua MnO
2
tao ra trong qua trinh chun trong mi trong trung tinh hoc kim anh
hong n vic xac nh im cui cua qua trinh chun .
D iu chinh mi trong acid, dung H
2
SO
chu khng dung HCl va HNO

3
vi:
- HNO
3
la cht oxi hoa manh, no s oxi hoa cht khu lam sai kt qua
chun .
- Khi trong dung dch co Cl
-
thi co phan ung xay ra nh sau:
10 Cl
-
2MnO
2
2-
1H
2Mn
2
Cl
2
H
2
O

Phan ung cam ung: la phan ung mt minh thi xay ra rt chm, nhng tc cua no
oc tng ln ng thoi co mt phan ung nhanh khac xay ra. (trang 2, TVNghi)
Kali pemanganat KMnO
khng phai la cht gc vi no thng khng tinh khit, bao

gio cung chua tap cht la san phm khu MnO
2
. Ngoai ra KMnO
la cht oxi hoa manh, d

khu boi cac cht huu c ln trong noc, trong bui khng khi, b phn huy boi anh sang,...
Do o dung dch KMnO
sau khi iu ch xong phai ung trong l co mau nu, y kin

va yn mt thoi gian moi oc dung. Troc khi dung phai xac nh lai nng bng
cht chun la acid oxalic.
Dung Kali pemanganat KMnO
cho phep xac nh oc nhiu cht v c va huu c

khac nhau bng cac cach chun khac nhau:
- cac cht khu: cac kim loai (Fe, Bi, Ag, Cd, n, kim loai t him,...), cac phi kim
(Sb, As, P,...), cac ion co hoa tr thp co kha nng cho hop cht cua nguyn t co hoa tr
cao (Fe
2
, Cr
2
, ...)
- cac cht oxi hoa: Fe
3
, Ce(V), (V), W(V), ...
Phng phap pemanganat co cac u im sau:
- khng phai dung cht chi th
- pemanganat co th oxi hoa khu cao
P E
Sn SnI
, 1
0
/
2

+
, nn co th xac nh oc
nhiu cht khi chung khng th chun oc bng cac cht oxi hoa yu.
- pemanganat re, d kim.
- xac nh oc ca nhung cht khng co tinh oxi hoa khu, vi du nh Ca
2
trong dung
dch (thm chi ca Pb
2
) bng cach kt tua voi oxalat sau o chun long cht khu d
hoc hoa tan kt tua s tinh oc long Ca.
2.2.3..2. Phng phap bicromat
Dy la phng phap chun oxi hoa khu dua trn phan ung oxy hoa cua ion
cromat Cr
2
O
2-
trong mi trong axit.
Cr
2
O
2-
e 1H
2Cr
3
H
2
O
P E
5r I 5r
3 , 1
0
2 /
3 2
2

+
Th oxi hoa khu
0
2 /
3 2
2
+
5r I 5r
E
cung phu thuc vao nng cua ion H
. K
2
Cr
2
O
oxi
hoa yu hn KMnO
.
Phng phap bicromat co nhung u im sau:
- K
2
Cr
2
O
d iu ch oc tinh khit, K
2
Cr
2
O

la cht gc nn dung dch iu
ch, d bao quan va bn lu.
- co th tin hanh chun trong cac dung dch acid H
2
SO
, H
3
PO
va ca trong HCl
C2M.
- Tuy dung dch K
2
Cr
2
O
co mau da cam nhng mt git dung dch chun sau im

tng ng khng u nhn ra su thay i vi cong mau rt yu, ngoai ra vi san
phm cua phan ung la Cr
3
co mau xanh tim nn lam cho su thay i mau khng r rt.
Vi vy khi chun bng dung dch K
2
Cr
2
O
ta phai dung cht chi th. Cht chi th

thong dung la diphenylamin (
0
0,V), mui natri hay bari diphenylaminsunIonat
(
0
0,V) (cht chi th nay d tan trong noc hn diphenylamin va su i mau r rt
hn (tu khng mau chuyn sang mau o). Cung co th dung acid phenylantranilic
(
0
1,0V) co dang oxi hoa mau tim cang dang khu khng mau.
- khi chun bng dung dch chun dicromat co th dung HCl lam mi trong ma
khng so gy sai s, vi nng HCl khng qua cao thi dicromat khng oxi hoa oc
clorua nh ion pemanganat.
- K
2
Cr
2
O
co kha nng oxi hoa oc nhiu cht v c va huu c: Fe(), Mn(),

Ti(), SO
3
2-
, Fe(CN)
-
,
-
, rou, acid ascobic, ....
- vi du: pp dicromat dung nh long rou etylic theo phan ung:
3C
2
H
OH 2Cr
2
O
2-
1H
Cr
3
3CH
3
COOH 11H
2
O
Phng phap oc tin hanh bng cach cho long dung dch chun dicromat tac
dung voi dung dch phn tich khi un nong, sau o chun ngoc long dicromat d
bng dung dch chun Fe
2
dung acid diphenylamin lam cht chi th.
Mt s phan ung c trng dung trong chun : trang 13, TTHiu
2.2.3..3. Phng phap iod/thiosunIat
Dua vao phan ung oxy hoa cua ion
3
-
:
3
-
2e 3
-
(
2
2e 2
-
)

P E
_ _
, 0
0
3 /
3

Dc im cua phng phap:
- D chun bng dung dch iot, ta iu ch dung dch chun bng cach pha dung
dch
2
trong long d K, do tan cua
2
trong noc kha nho.
- od khng phai la cht gc. Ngoai ra, dung dch
3
-
cung khng co nng n nh
theo thoi gian do iod co th b thng hoa va thong d b khu boi cac cht huu c, boi
bui. Ngoai ra iotdua trong dung dch chun cung d b oxi hoa boi oxi trong khng khi:
-
O
2
H
2
2
2H
2
O
Do o troc khi dung voi vai tro cua dung dch chun cn xac nh lai nng cua dung
dch bng thiosunIat bit chinh xac nng .
Trong phng phap nay ngoi ta thong dung phan ung cua thiosunIat (S
2
O
3
2-
), vi
th phng phap nay thong co tn gi ghep la iot-thiosunIat. Phan ung giua iot va
thiosunIat xay ra theo phng trinh sau:
2S
2
O
3
2-

2
2
-
S
2-
on thiosunIat ion tetrathionat
P E
I a I a
1 , 0
0
2 /
2
3 2
2

2
2e 2
-

2
2
_
S
7
2S
2
O
3
2-
-2e S
2-

2
3 2
I a
S 7
D nhn bit im cui cua qua trinh chun ngoi ta dung cht chi th la h tinh bt.
H tinh bt khng phai la cht chi th oxi hoa khu ma no co tinh cht hp phu
2
, co mau
xanh m.
Khi su dung cht chi th h tinh bt, ta phai lu y, nu dung dung dch
2
chun
Na
2
S
2
O
3
thi ta co th thm cht chi th h tinh bt ngay tu u, trong qua trinh chun
dung dch khng mau, sau im tng ng, co d mt git dung dch
2
, dung dch
s chuyn sang mau xanh.
Nhng khi chun dung dch
2
bng Na
2
S
2
O
3
thi khng oc cho cht chi th h
tinh bt ngay tu u, boi vi nu thm h tinh bt tu u, no s hp phu
2
,
2
b hp phu
ln h tinh bt g giai hp phu rt chm nn khi chun long Na
2
S
2
O
3
d ma mau
xanh vn cha mt. Do o chun s qua im tng ng rt nhiu nn kt qua sai.
Nn khi chun
2
bng dung dch Na
2
S
2
O
3
chi oc thm h tinh bt khi qua trinh
chun gn kt thuc nghia la khi dung dch con lai rt it
2
(dung dch luc o co mau
vang rt nhat, nh mau rm nn gi la mau vang rm). Khi chi h tinh bt vao thi dung
dch s co mau xanh , nho tu tu tung git dung dch Na
2
S
2
O
3
, vua nho vua lc manh n
khi dung dch mt mau xanh thi o la im cui cua su chun .
- Th oxi hoa khu nm o khoang giua bang th oxi hoa khu tiu chun nn:
nhung cht co
0
~0, V co kha nng b khu boi iod
nhung cht co
0
0, V co kha nng b oxi hoa boi
2
tu do.
ac nh cht khu:
Co th xac nh truc tip cac cht khu bng cach cho tac dung voi
2
. Nhn ra im
tng ng bng su i mau cua dung dch: khi khng co
2
dung dch co mau vang
nhat. Thng thong dung chi th h tinh bt: khi co iod d s tao voi h tinh bt mt cht
mau xanh lam.
Cung co th dung
2
xac nh nhiu cht khu bng phng phap chun ngoc,
nguyn tc nh sau: thm mt long d dung dch
2
bit nng xac nh vao dung
dch cht khu, sau khi phan ung xay ra hoan toan, ta chun long
2
d bng dung dch
chun thiosunIat.
Vi du: xac nh SO
3
2-
, AsO
3
3-
, H
2
S, Sn
2
SO
3
2-

2
H
2
O SO
2-
2
-
2H
AsO
3
3-

2
H
2
O AsO
3-
2
-
2H
H
2
S
2
S 2
-
2H
Sn
2

2
Sn
2
-
ac nh cht oxi hoa:
Thong dung phng phap th: cho thua K vao cht oxi hoa cn chun o mi
trong acid thi phan ung s giai phong mt long tng ng
2
. Long iod sinh ra nay
oc nh long bng dung dch thiosunIat bit nng , tu o tinh oc cht oxi hoa
cn xac nh
Khi nh long cac cht oxi hoa bng phng phap iod, cn phai cho thua K
phan ung giua K va cht oxi hoa xay ra hoan toan va khi
2
giai phong s d dang hoa tan
vao trong dung dch noc do phan ung tao phuc kem bn
3
-
.
2

-

3
-
Sau o chun long
2
thoat ra (o dang
3
-
) bng dung dch chun Na
2
S
2
O
3
.
Bng cach nay co th xac nh oc cac cht oxi sau: Br
2
, MnO
-
, Cr
2
O
2-
, ClO
3
-
,
H
2
O
2
, Fe
3
, ...
Br
2
2
-
2Br
-

2
2MnO
-
10
-
1H
2Mn
2

2
H
2
O
2Fe
3

-
2Fe
2

2
m P) iotXtio@unu.t !1n :"P! dvng :t e(! :nh .!id. odua phan ung voi iodat khi
co acid theo phng trinh:
-
O
3
-
H
3
2
H
2
O
Tu phng trinh nay ta thy long ion H
tham gia phan ung tng ng voi long

2
thoat ra. Do o sau khi phan ung trn xay ra hoan toan, ta chun long
2
thoat ra bng
dung dch thiosunIat tiu tn ta s tinh oc long ion H
trong dung dch. Nho o xac

nh oc acid. PP nay gi la pp iot-thiosunIat xac nh acid.
Chun acid ascobic (CHO):
C

2
C
2
-
2H
Chu y:
- natri thiosunIat co th kt tinh tinh khit, ung voi cng thuc
Na
2
S
2
O
3
.H
2
O nhng no vn khng phai la cht gc vi dung dch
Na
2
S
2
O
3
khng bn, nng cua no bi thay i theo thoi gian do tac
dung cua CO
2
va O
2
cua khng khi:
Na
2
S
2
O
3
CO
2
H
2
O NaHCO
3
NaHSO
3
S.
Na
2
S
2
O
3
O
2
Na
2
SO
S.
- Khi su dung iot-thiosunIat cn chu y cac im sau:
phai chun trong mi trong kim yu co pH.
Vi trong mi trong kim manh co phan ung sau:
2
2OH
-
O
-

-
H
2
O
O
-
tao thanh co tinh oxi hoa manh. No oxi hoa mt phn S
2
O
3
2-
b chuyn thanh
SO
2-
cang nhiu. Do phan ung phu nay nn khng th tinh chinh xac kt qua
phn tich oc.
S
2
O
3
2-
O
-
2OH
-

-
2SO
2-
H
2
O
Nu phan ung sinh ra H
s lam pH cua dung dch giam khng am bao mi

trong kim, ta phai dung NaHCO
3
lam cht m ly bot H
trong dung dch

di: HCO
3
-
H
CO
2
H
2
O.
- Chun iot thiosunIat khng oc dung khi un nong, vi iot la cht d
bih thng hoa va kha nng hp phu cua h tinh bt voi
2
giam khi
nhit tng.
- Vi iot tan it trong noc nhng tan nhiu trong dung dch co d
-
do
phan ung:
-

2

3
-
- Do o khi xac nh cht oxi hoa bng phep o iot phai dung d K.
Phan ung nay la phan ung thun nghch va ion
3
-
rt kem bn nn
khi chun
2
bng thiosunIat cn bng b pha v va dch chuyn
cn bng v phia trai, toan b long
2
thoat ra oc thiosunIar phan
ung ht.
- Phan ung giua
-
voi cac cht oxi hoa va phan ung giua
2
voi cht khu
thong xay ra chm, do o sau khi thm
-
hay
2
vao ta phai cho
khoang phut phan ung xay ra hoan toan ri moi tin hanh chun
. Khi yn dung dch phai y kin va t o ch ti vi anh sang
lam tng phan ung oxi hoa
-
thanh
2
boi oxi cua khng khi:
2
-
H
O
2

2
2H
2
O
2.2.3.. Vi du nh long bng phng phap chun oxy hoa khu
2.2.3..1. ac nh nng KMnO
theo cht gc TK
2.2.3..2. Dnh long Fe
2
Nguyn tc: trong mi trong acid (acid sunIuric), ion Fe() s b pemanganat oxi
hoa ln st , im tng ng nhn oc nhn oc khi d mt git dung dch chun
kali pemanganat, dung dch co mau hng nhat (bn trong 30 giy).
Phan ung chun :
MnO
2-
Fe
2
H
Mn
2
Fe
3
H
2
O.
vy ,3ng KLng chu|n 9*
v ong cong chun V
0
ml dung dch Fe
2
, nng C
0
(M) bng dung dch
chun KMnO
nng C (M).
MnO
2-
e H
Mn
2
H
2
O , z, DM/
Fe
2
- 1e Fe
3
x , z1, DM
Trong o th tiu chun cua h nh sau:
,
[ ]
[ ]
[ ]
[ ]
+
+
+
+
+
+
+ +
2
3
2
3
0
/
lg 0 , 0 , 0
lg 0 , 0
2 3
Fe
Fe
E
Fe
Fe
E E
Fe Fe
- tinh V
t
:
0 0
2
2
P 5
5P
6.n,.u lu-ngcu.Fe s-%-l,u-ng
the%1.- I lu-ngcu.Sn s-%-l,u-ng
F
+
Tai im tng ng F1 hay

1
0 0
2
2
P 5
5P
6.n,.u lu-ngcu.Fe s-%-l,u-ng
the%1.- I lu-ngcu.Sn s-%-l,u-ng
F
t
5
P 5
P P 5 5P
t t
0 0
0 0

- Khi C
N
.V
0
X
5
. V
0
, F1, troc im tng ng. Nng cua Fe
2
va Fe
3
d
tinh hn nn tinh in th dung dch theo Fe:
[ ]
[ ]
+
+
+
+ +
2
3
0
/
lg 0 , 0
2 3
Fe
Fe
E E
Fe Fe
,
_
+
+
+
+ +
5P P 5
P P
P P
5P
E E
Fe Fe
lg 0 , 0
0 0
0
0
0
/
2 3
,
_
+
+ +
5P P 5
5P
E E
Fe Fe
lg 0 , 0
0 0
0
/
2 3
Trong o:
[ ]
0
3
P P
P 5
Fe
X
+
+
,
0
0
P 5
P 5
F
X
X
F
F
E E
Fe Fe
+
+ +
1
lg 0 , 0
0
/
2 3
- Khi C
N
.V
0
X
5
. V
0
- im tng ng, khi o
Fe
3
Mn
2
Fe
2
MnO
2-
[ ]
[ ]
+
+
+
2
2
0
/
lg
0 , 0
2 2
Sn
SnI
E E
Sn SnI
t
x

[ ]
[ ]
+
+
+
+ +
2
3
0
/
lg 0 , 0
2 3
Fe
Fe
E E
Fe Fe
t
D tinh
t
ta cng hai phng trinh trn, khi o ta co:
[ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ] [ ]
+ +
+
+
+
+
+ +
+ + +
+ + +
+ + +
2 2
3 2
0
/
0
/
2
3
2
2
0
/
0
/
lg 0 , 0
lg 0 , 0 lg 0 , 0
2 2
2 3
2 2
2 3
Fe Sn
Fe SnI
E E E
Fe
Fe
Sn
SnI
E E E
Sn SnI Fe Fe
t
Sn SnI Fe Fe
t
0
/
0
/
2 2
2 3 + + +
+
Sn SnI Fe Fe
t
E E
E
- Khi C
N
.V ~
0
X
5
. V
0
, F~1 sau im tng ng, khi o:
[ ]
[ ]
+
+
+
2
2
0
/
lg
0 , 0
2 2
Sn
SnI
E E
Sn SnI
t
) 1 lg( 0 , 0
0
/
2 2
+
+
F E E
Sn SnI
2.2.3..3. Dnh long Fe
3
(TT Hiu, trang 11)
Nguyn tc:
- Troc ht phai khu Fe() thanh Fe() bng SnCl
2
d it trong iu kin un
nong toi 0-0 C.
- Sau o loai bo SnCl
2
bng dung dch HgCl
2
, san phm tao thanh la calomen
Hg
2
Cl
2
giai lua trng:
HgCl
2
SnCl
2
Hg
2
Cl
2
SnCl
.
Nu khng co kt tua xut hin thi chung to SnCl
2
b thiu, nu tao thanh kt tua
trng bng hoc mau xam en thi chung to cho qua nhiu SnCl
2
.
SnCl
2
HgCl
2
Hg(en) SnCl
.
Trong ca hai trong hop u phai tin hanh thi nghim lai tu u.
- Tin hanh chun bng KMnO
cho n khi xut hin mau hng nhat b vung.

*** Diu kin: phai co su co mt cua hn hop bao v ymmerman.
2.2.3... Dnh long Ca
2
TK
2.2.3... ac nh nng Na
2
S
2
O
3
theo cht gc TK
2.2.3... ac nh nng
2
bng dung dch chun Na
2
S
2
O
3
TK
2.2.3... Dnh long acid ascobic (C
) TK
/./.O. Ph"%ng )h() !huhn :C )h3! !h9t
2.2..1. C so ly thuyt va nguyn tc cua cac phng phap chun phuc cht
(complexon, phng phap bac, phng phap thuy ngn) TK
Phng phap chun phuc cht dua trn phan ung tao thanh cac phuc cht tan
hoc cac mui it phn li. Cac phan ung tao phuc dung trong chun phuc cht phai thoa
mn cac yu cu cua cac phan ung dung trong phn tich th tich. Do phai thoa mn cac
yu cu trn, s phan ung oc dung trong chun phuc cht rt han ch.
Trong phn tich th tich, ngoi ta thong dung cac phng phap chun tao phuc
sau y:
chu|n 9 ph]c ch[t 1f ph= t/ l< ch[t 1 cU*
Phng phap thuy ngn : pp nay dua trn phan ung tao phuc bn giua ion Hg
2
voi
cac anion clorua, bromua, iodua va xianua. Vi du:
Hg
2
Cl
-
HgCl
HgCl
Cl
-
HgCl
2
Hg
2

-
Hg
Phng phap bac: pp nay dua trn phan ung tao phuc giua ion Ag
va ion xianua.
Ag
2CN
-
Ag(CN)
2
-
chu|n 9 ph]c ch[t 1f ph= t/ l< ch[t hVu cU #c-%pleZ-n)*
Phng phap complexon: La phng phap chun dua trn phan ung tao hop cht
ni phuc cua nhiu ion kim loai voi mt s thuc thu huu c gi chung la complexon.
2.2..2. Cac k thut chun thong dung trong chun phuc cht
Trang 1 ... Tu Vng Nghi
a) chun truc tip:
cach chun nay dung chun nhung ion kim loai khi tao oc iu kin
chun phan ung chun thoa mn cac iu kin cua phan ung chun th tich.
Theo cach nay ta dung dung dch chun trilon B chun truc tip cac kim loai cn
phn tich. Troc khi chun cn a pH cua dung dch v gia tr thich hop cho su tao
phuc (thong dung dung dch m).
b) chun ngoc:
cach nay dung khi cac ion kim loai khng th chun bng pp truc tip, chng han
nh khng tim oc cht chi th thich hop, khng giu oc cac ion kim loai trong dung
dch o pH cn thit cho vic chun hay tc phan ung giua ion kim loai voi trilon B
xay ra qua chm.
Nguyn tc cua cach chun nay la thm vao dung dch mt long d xac nh
dung dch chun trilon B, tao mi iu kin (pH, nhit , thoi gian,...) phan ung xay
ra hoan toan. Sau o tin hanh chun long trionlon B d bng dung dch chun mui
cua kim loai ( n
2
, Mg
2
, Fe
3
, ...) voi pH va cht chi th thich hop.
e) chun th hay chun y
Mt s ion kim loai tao phuc complexonat bn hn rt nhiu phuc conplexonat
magie, nhng vi li do nao o khng th chun truc tip oc, ta co th chun
cac ion kim loai o bng phng phap y (th).
d) chun ion H
oc thay th khi tao complexonat bng dung dch chun baz

trong qua trinh tng tac cua trilon B voi cation kim loai nao o lam tach ra mt
long ng ng ion hidro.
Ngoi ta chun lai long ion hidro bng dung dch chun kim manh voi cht chi th
acid baz nh metyl o hoc chun bng phng phap iot - thiosunIat.
e) chun cac anion bng complexcon
cac anion khng phan ung truc tip voi trilon B nn chi co th chun bng cach
gian tip theo cach sau:
- kt hop phan ung kt tua voi complexon: nguyn tc cua pp nay la kt tua anion
cn nh long bng mt cation kim loai thich hop, sau o chun long cation kim
loai d trong kt tua bng trilon B ri tu o tinh ra long anion cn xac nh.
u cu cua phng phap nay la kt tua co thanh phn ung cng thuc, tan nho,
tinh khit. Nu tan cua kt tua trong trilon B khng ang k thi co th tin hanh chun
lng ion kim loai d trong dung dch ma khng cn tach kt tua. Song nu tan cua
kt tua trong trilon B ang k thi pha lc bo kt tua ri moi chun long ion kim loai
d trong noc lc, hoc em hoa tan kt tua bng dung mi thich hop ri chun long
ion kim loai co trong kt tua.
- kt hop phan ung tao phuc voi chun conplexon. Nguyn tc cua pp nay la
dung mt mui kim loai thich hop (dung d chinh xac) cho tao phuc voi anion cn xac
nh, sau o chun long cation kim loiaj d bng trilon B ri tu o tinh ra long
anion ban u.
u cu cua pp nay la phuc cua cation kim loai voi anion cn xac nh phai bn hn
phuc complexonat cua kim loai.
- kt hop phan ung oxi hoa khu voi phan ung chun complexcon. Di voi nhung
anion co th khu hoc oxi hoa chuyn no thanh cation thi nn dung nhung cht oxi hoa
hay khu thich hop chuyn no thanh cation ri chun cation tao thanh bng trilon B,
tu o suy ra long anion cn xac nh.
2.2..3. Phng phap chun complexon
2.2..3.1. Khai nim v complexon
Complexon la tn gi chung chi cac thuc thu la dn xut cua acid amino axetic.
Cac dn xut quan trng nht oc dung nhiu trong phan ung tao phuc voi ion kim loai
la:
- mui inatri cua acid amino triaxetic (complexon , trilon A), vit tt la H
3
:
Complexon tao phuc kem bn voi ion kim loai nn it dung.
- Complexon (chelaton , trilon B) la axit etylen diamin tetraaxetic (DTA), ki
hiu : H
, it tan trong noc.

- Complexon (trilon B) : mui dinatri cua axit etylen diaminotetra axetic (mui
dinatri cua DTA), ki hiu : Na
2
H
2
, trong phong thi nghim vn hay quen gi la DTA.
Cac phan ung tao phuc cua cac complexon va cac cation kim loai xay ra tng tu
nhau nhng co bn khac nhau. Trong s cac complexon thi complexon tng i d
iu ch va kha nng tao phuc cung tt, nn thong oc dung hn. Phng phap chun
complexon cung thong dung dung dch chun la trilon B.
DTA it tan trong noc, vi vy thong dung doi dang mui Na
2
H
2
. Trong phn
tich, DTA va Na
2
H
2
ngoai su khac nhau v tan va khi long mol, con lai cac tinh
cht hoa hc nht la tinh tao phuc khng co su phn bit, nn thong vn gi chung la
DTA.
DTA coa kha nng tao phuc voi hu ht cac ion kim loai (tru cac kim loai kim) va
tuy theo pH cua dung dch co th biu din bng phng trinh khac nhau (do DTA tn
tai trong dung dch doi dang H
, H
3
-
, H
2
2-
, H
3-
,
-
phu thuc vao pH). Du phng
trinh phan ung khac nhau nhng co im chung la ti l mol giua DTA va ion kim loai
lun la 1:1 va giai phong ra toan b long H
co trong thanh phn tn tai cua DTA.

DTA la acid a chuc co:
H
H
3
-
H
K
a1
10
-2
H
3
-
H
2
2-
H
K
a2
10
-2,
H
2
2-
H
3-
H
K
a3
10
-,1
H
3-

-
H
K
a
10
-10,2
Phan ung tng quat cua ion kim loai M
n
voi DTA:
M
n
H
2
2-
M
(n-)
2H
pH -
M
n
H
3-
M
(n-)
H
pH -10
Vic giai phong H
trong qua trinh tao phuc la cho pH cua dung dch thay i trong
qua trinh chun , do o co th anh hong nhiu n kha nng tao phuc cua cac ion kim
loai. Cho nn trong qua trinh chun phuc cht, giu cho pH cua dung dch o mt
khoang nht nh thich hop cho su tao phuc, ta thong dung mt long dung dch m.
Dong chun :
Cn bng tao phuc:
M M
Cac cn bng cua nc phn ly cua acid H
:
H
H
3
-
H

H
3
-
H
2
2-
H

H
2
2-
H
3-
H

H
3-

-
H

Cac cn bng phu cua kim loai M
n
voi cac ion khac trong dung dch nh OH
-
hoc
thanh phn dung dch m nh NH
3
:
MOH
-
MOH
MOH OH
-
M(OH)
2
Phng trinh ong nh phn:
[ ]
[ ]
[ ]
0 0
0

0
0 0
1
P 5
P P
S
S
S
P P
P 5
F
+
,
_
Voi M
`
va
`
la tng cac dang nng cn bng cua cac dang ion kim loiaj M va
DTA tru phuc M giua M va .
Troc im tng ng:
[ ]
[ ]
[ ]
0 0
0

0
0 0
1
P 5
P P
S
S
S
P P
P 5
F
+
,
_
2.2..3.2. Cht chi th trong phng phap complexon

Loai cht chi th oc dung nhiu nht trong phng phap complexon la cac cht
mau huu c (co tinh acid hoc baz yu), chung co kha nng tao thanh phuc mau voi ion
kim loai (gi la cht chi th kim loai). Trong iu kin xac nh mau cua phuc o khac
voi mau cua cht chi th tu do. Trong phn tu cht chi th kim loai cung co nhom mang
mau va tro mau nn cung la cht chi th pH.
Cac cht chi th kim loai thong dung trong pp complexon phai thoa mn cac yu
cu sau:
- phuc cua chi th voi ion kim loai pha kem bn hn phuc complexonat voi kim loai
(
Me
~
Mend
).
- mau cua phuc giua cht chi th voi ion kim loai phai khac voi mau cua cht chi th
tu do trong iu kin tin hanh chun .
- su i mau xay ra nhanh va r rt, gn im tng ng cua qua trinh chun .
- cht chi th phai co phan ung c trng ring voi ion kim loai cn xac nh.
Cac cht chi th kim loai oc dung ph bin trong phng phap chun
complexon la:
Er-cr-% en T #ETRII) #5
EQ
J
&F
I
(
X
F
a)* La chi th thuc nhom phm mau azo,
oc su dung nhiu nht. Mau o khi tn tai trong dung dch co pH .
La mt acid ba nc, nc 1 kha manh (SO
3
H), nc 2 va 3 co hng s phn li tng
ung la pK
2
,3, pK
3
11,. O pH -10 chi th co mau xanh, phuc cht voi Mg
2
, n
2
,
Pb
2
, . co mau o.
Ki hiu H
2
n
-
(mang in tich m vi trong noc nhom sunIo phn li).
H
2
n
-
Hn
2-
n
3-
o xanh da cam
Hn
2-
M
2
Mn
-
H
xanh o
SureZt #5
'
J
'
I
t
X
t
.EJ
E
I)
Thuc nhom phm mau azo va cung hay oc su dung. Anion murexit co mau o tim.
Ky hiu : H
n
-
. Bn nguyn tu hydro trong ky hiu la proton cua cac nhom amino.
H
3
n
2-
M
2
MH
2
n
-
Mau CaH
2
n
-
: o; CuH
2
n
-
, NiH
2
n
-
, CoH
2
n
-
: vang.
Khi chun voi chi th murexit thong dung mi trong pH 10-11 chi th
giai phong co mau tim H
3
n
2-
la su chuyn mau r nht.
D thy r su chuyn mau cua cht chi th kik loai trong chun complexon, ta
ly mt vi du cu th nh sau: khi chun Mg
2
bng trilon B o pH 11 dung cht chi th
la eriocrom. Toan b qua trinh chun oc m ta bng s sau:
- Cho chi th (riocrom en T) vao dung dch chua ion kim loai thi ion kim loai phan ung
voi chi th cho ra dung dch mau o:
Mg
2
Hnd
2-
Mgnd
-
H
o vang
- Sau o chun dung dch chua ion kim loai bng Trilon B thi ion kim loai tu do s phan
ung voi Trilon B:
Mg
2
H
3-
Mg
2-
H
- Sau khi ht ion kim loai tu do thi:

H
3-
Mgnd
-
Mg
2-
Hnd
2-

o vang xanh
Khi dung dch chuyn tu o nho sang xanh da troi thi ung chun .
2.2..3.3. Phng trinh ong nh phn va sai s chi tr trong chun complexon
Dong nh phn la ong biu din su bin thin cua pM theo ti phn chun F,
pMI(F), trong o pM-lgM, va FCV/C
0
V
0
la %]c 9 lKng -n k% l-8 x Kc
chu|n 9 h.y l< phWn -n k% l-8 x t8- ph]c 1f c-%pleZ-n.
Trong qua trinh chun trong dung dch co cac cn bng sau:
- cn bng tao phuc giua
-
va ion M
n
, n gian ta khng vit in tich cac ion.
M M
- cac cn bng cua nc phn li cua acid H
-
H
H
3-
H
3-
H
H
2
2-
H
2
2-
H
H
3
-
H
3
-
H
- cac cn bng tao phuc phu cua M

n
voi cac ion khac co trong dung dch nh OH
-
,
hoc la mt thanh phn cua dung dch m:
M OH
-
MOH
MOH OH
-
M(OH)
2
...........
Dong chun 2,00 ml dung dch n
2
bng DTA 10-10M trong m
NH
3
/NH
Cl trong o NH
3
0,100M
Nhn xet:
Dong chun cung co dang tng tu cac ong chun theo pp khac.
O gn im tng ng co boc nhay chun . Boc nhay chun phu thuc
vao nng cua DTA va hng s bn iu kin cua phuc tao boi DTA voi ion kim
loai. Khi cac ai long o cang lon thi boc nhay cua ong nh phn cang dai.
Sai s chun : Gi S la sai s chun va S F-1
2.2..3.. Chun hn hop nhiu ion cac cht che TK Trang 1... Tu Vng
Nghi
2.2... Vi du nh long bng phng phap chun complexon
a. Dnh long ion Ca
2
, Mg
2
, hn hop (Ca
2
va Mg
2
) - TK
b. Dnh long cung cua noc - TK
c. Dnh long ion Ba
2
va SO
2-
- TK
d. Dnh long ion n
2
, Fe
3
, Al
3
va hn hop (Fe
3
va Al
3
) - TK
/./.[. Ph"%ng )h() !huhn :C 6?t t5.
2.2..1. Nguyn tc cua phng phap
Phng phap chun kt tua dua trn vic su dung cac phan ung tao thanh cac hop
cht kho tan (kt tua).
2.2..2. u cu i voi phan ung chun kt tua
Cac phan ung kt tua oc su dung phai thoa mn cac iu kin sau:
- kt tua oc tao thanh trong phan ung chun phai thuc t khng tan, tuc la phan
ung xay ra hoan toan va theo mt ti long xac nh.
- tc tao thanh kt tua phai u lon, tuc la khng tao thanh dung dch qua bo hoa.
- phan ung phai chn lc, nghia la anh hong cua cac qua trinh cng kt, hp phu,
kt tua theo phai khng ang k.
- phai co cht chi th thich hop xac nh oc im tng ng.
Tuy s long cac phan ung kt tua rt nhiu nhng chung thong khng thoa mn
cac yu cu trn, nn a s cac phan ung o ung dung trong phn tich nh tinh, con rt it
oc ap dung trong phn tich nh long. Trong thuc t ngoi ta thong dung cac phan
ung kt tua sau:
Ta chi xet trong hop thu nht.
2.2..3. Phng trinh ong nh phn va sai s chi tr trong chun kt tua
Vi du: chun V
0
ml dung dch chua halogenua
-
nng C
0
(mol/l) bng dung
dch chun AgNO
3
nng C (mol/l)
Dong chun : la ong biu din su phu thuc cua p ( cht cn phn tich),
hay pMe (Me cht chun) vao th tich cht chun thm vao.
Phan ung chun :
Ag

-
Ag
Tinh V
t
:
V
t
. C C
0
.V
0
V
t
C
0
.V
0
/C
0 0
P 5
5P
F
[ ][ ]
"gv
T v "g
+
[ ]
P P
P 5
v
+
+
0
0 0
(*)
[ ]
P P
5P
"g
+
+
+
0
(**)
Ly (**) - (*) ta co:
[ ] [ ]
P P
P 5
P P
5P
v "g
+
+

+
0
0 0
0
[ ] [ ]
P P
P 5 5P
v "g
+

+
0
0 0
[ ] [ ] ( ) 1
0 0
0

+
+
F
P 5
P P
v "g
[ ]
[ ]
0 0
0
1
P 5
P P
"g
T
"g F
"gv
+
,
_

+
+
Voi la s mol cua kt tua ung voi 1 lit dung dch.
Cng thuc tinh p trong cac giai oan chun nh sau:
- troc im tng ng:
) 1 lg( lg
0
0 0
F
P P
P 5
pv
+

- tai im tng ng:
"gv
pT pv
2
1
- sau im tng ng:

P P
P 5
F pT pv
"gv
+
+ +
0
0 0
lg ) 1 lg(

Nhn xet:
- dang ong chun ging nh ong cong chun acis baz va ong chun
ong chun trong phng phap oxi hoa khu o gn im tng ng co boc nhay.
- nng cht kt tua cang lon, tich s tan cua kt tua cang nho bc nhay trn
ong chun cang dai va ngoc lai. Dong chun chi co boc nhay khi T_10
-10
va
nng C~10
-2
M.
2.2... Cac phng phap chun kt tua
2.2...1. Phng phap Mohr (Mo)
Nguyn tc: thm vao dung dch phn tich mt ion gi la ion chi th, ion nay co kha
nng tao voi ion Ag
mt kt tua co mau, xut hin o im cui chun . Va ion kim

loai oc Mohr su dung trong qua trinh chun Br
-
, Cl
-
o la CrO
2-
. CrO
2-
tao voi ion
Ag
mt kt tua mau o gach.

Phan ung chun : Ag
Cl
-
AgCl trng T
AgCl
10
-10
Nhn ra im tng ng:
2Ag
CrO
2-
Ag
2
CrO
nu o T
Ag2CrO
2.10
-12
Diu kin ap dung:
- nng cht chi th K
2
CrO
cn 2.10
-
2 M, nhng tt nht la 10
-2
n 10
-3
M vi
khi o s tranh oc mau vang m cua K
2
CrO
lam kho khn cho vic nhn ra lt tua

Ag
2
CrO
.
- pH mi trong tt nht la -10, vi nu acid qua s khng tao oc kt tua
Ag
2
CrO
, do 2CrO
2-
2H
Cr
2
O
2-
H
2
O chuyn dch v phia Cr
2
O
2-
. Nu qua kim
s co kt tua cua Ag
2
voi OH
-
.
Ag
OH
-
AgOH
2 AgOH Ag
2
O H
2
O
- cn phai loai cac ion can tro nh :Ba
2
, Pb
2
, Bi
3
(vi chung tao kt tua voi CrO
2-
);
S
2-
, SO
2-
, PO
3-
, C
2
O
2-
(vi chung tao kt tua voi Ag
).
-Dung dch chun AgNO
3
bao gio cung chua o buret.
- phng phap Mo chi dung xac nh Br
-
, Cl
-
, nhng khng dung chun
-
,
SCN
-
oc vi co hin tong hp phu kha r, do o gy ra sai s lon.
2.2...2. Phng phap Volhard (Vonha)
Nguyn tc: thm d chinh xac mt long dung dch chun AgNO
3
vao dung dch
halogenua cn chun Ag
kt tua ht voi cac anion halogenua, ri chun long

Ag
d bng dung dch chun SCN

-
voi cht chi th la ion Fe
3
(phn st ). Khi Ag

chun ht, mt git SCN
-
d s tao voi ion Fe
3
tao thanh phuc FeSCN
2-
co mau o
nn lam dung dch co mau hng.
Phan ung chun : Ag
Cl
-
AgCl trng T
AgCl
10
-10
Ag
CNS
-
AgCNS trng T
AgCNS
10
-12
Fe
3
CNS
-
FeCNS
2

o 10
2
Chu y:
- Phng phap nay thuc hin trong mi trong acid tranh Fe
3
b thuy phn.
- Phng phap nay co th dung xac nh Br
-
,
-
, SCN
-
.
- khi nh long Cl
-
co hin tong mau chuyn khng r rang, mau khng bn, khi
mau bn vung thi qua im tng ng nhiu gy sai s lon. Ly do vi T
AgCl
10
-
10
~T
AgCNS
10
-12
nghia la kt tua AgCNS bn vung hn nn co phan ung:
AgCl CNS
-
AgCNS Cl
-
lam dch chuyn cn bng phn ly phuc v phia
phai:
FeCNS
2
CNS
-
Fe
3
lam mt mau o.
D khc phuc sai s nay phai loai bo kt tua AgCl, ri sau o moi nh long Ag
d
o phn noc lc. Hoc cho vao h mt dung mi huu c khng trn ln voi noc
(benzene, chloroIorm, ether, .) lam von kt tua AgCl trn b mt phn cach giua 2
lop noc dung mi huu c va do o ngn khng cho kt tua AgCl tac dung voi CNS
-
(lam chm qua trinh phn li cua AgCl va ngn can AgCl tip xuc voi SCN
-
).
- Khi nh long
-
khng oc cho chi th Fe
3
vao dung dch nh long troc khi
cho Ag
d ( tranh phan ung Fe

3

-
Fe
2

2
xay ra.
u im:
- nh phn trong mi trong axit do AgSCN khng tan trong axit nn ta co th dung
nh phn bac trong hop kim oc pha mu bng axit manh.
- Cac ion Ba
2
, Pb
2
khng gy can tro trong phng phap nay.
Cac ion can tro: mui thuy ngn () tao kt tua voi SCN
-
, cac cht oxy hoa s oxy
hoa SCN
-
, cht co kha nng tao phuc bn voi Fe
3
nh PO
3-
, F
-
.
2.2...3. Vi du nh long bng phng phap chun kt tua - TK
/.3. Ph"%ng )h() )hn t*!h trkng ;"Png
2.3.1. Nguyn tc cua phng phap phn tich trng long
Phn tich khi long la phng phap nh long hoa hc trong o ngoi ta o chinh
xac bng cach cn khi long cua cht cn xac nh hoc nhung hop phn cua no
oc tach ra o trang thai tinh khit hoa hc hoc la doi dang hop cht co thanh phn bit
troc.
u im:
- co chinh xac cao (co th doi 0,01)
- n gian v nguyn tc, dung cu phn tich thng thong
- ap dung nhiu i tong, gioi han ham long rng
- ung va lp lai tt (nu cn thn)
Nhoc im:
- qua trinh phn tich lu, trai qua nhiu giai oan, ng tac phn tich phuc tap,nc
bit khi xac nh cac long nho cac cht.
Vi vy pp nay chi dung trong nhung trong hop phep phn tich oi hoi chinh xac
cao nh kim tra ham long cac nguyn t trong mu chun, kim tra nng dung dch
chun.
Phn loai:
a) phng phap kt tua: Kt tua nguyn t cn xac nh doi dang hop cht kho tan
bng thuc thu thich hop, lc, rua sach kt tua ri m sy, nung kt tua n khi long
khng i, cn chinh xac khi long trn cn phn tich. Tu long cn va cn cu vao cng
thuc hoa hc cua dang cn ta s tinh oc ham long cua nguyn t cn xac nh.
Dang kt tua hinh thanh sau phan ung kt tua gi la ,8ng tB..
Dang kt tua vui cung m cn la ,8ng cn.
Dang tua va dang cn co th ging nhau nhng cung co th khac nhau.
Phng phap kt tua la phng phap oc su dung ph bin nht trong phn tich
khi long.
Vi du: D xac nh Mg, ngoi ta tin hanh nh sau: hoa tan mu phn tich trong
dung mi thich hop chuyn toan b long Mg vao dung dch doi dang ion Mg
2
. Tip
tuc xu ly dung dch bng cac thuc thu thich hop kt tua hoan toan va chn lc ion
Mg
2
doi dang hop cht kho tan MgNH
PO
. Lc, rua kt tua va sy no o nhit thich

hop chuyn hoan toan thanh hop cht Mg
2
P
2
O
. Cui cung cn xac nh khi long

cua no. Dua vao cng thuc cua kt tua va khi long vua cn oc s tinh oc ham
long cua Mg trong mu phn tich. Trong thi du nay hop cht MgNH
PO
oc kt tua
tach nh long Mg oc gi la ,8ng kt tB., con Mg
2
P
2
O
hop cht oc tao thanh

sau khi nung dang kt tua va em cn xac nh ham long cua Mg oc gi la ,8ng
cn.
b) Phng phap bay hi (pp ct): trong trong hop nay, mt hay nhiu hop phn cua
mu oc lam cho bay hi co th chuyn thanh mt cht bay hi.
Pp bay ct truc tip: Cu tu bay hi cn xac nh oc hp thu truc tip bng cht
hp thu c bit. Dua vao su tng khi long cht hp thu tinh oc long cu tu cn xac
nh.
D xac nh CO2 trong qung cacbnat ngoi ta phn huy long mu CaCO
3
bng
axit trong mt dung cu ring. Toan b long khi CO
2
giai phong ra oc hp thu ht vao
hn hn CaO NaOH ung trong mt binh ring. Long CO
2
o oc xac nh theo
tng khi long cua binh ung hn hop hp thu, phng phap xac nh ham long CO
2
nh trn gi la phng phap ct.
X pp ct gian tip:
Su dung khi mun xac nh m, hay noc kt tinh trong cac tinh th. Sau khi ct
hoan toan cht cn xac nh, hiu s troc va sau khi ct chinh la long cht cn xac
nh.
c) Phng phap tach: Cu tu cn xac nh oc tach ra doi dang tu do va oc cn
trn cn phn tich.
2.3.2. Cac yu cu dang tua va dang cn
2.3.2.1. u cu dang tua
D phng phap phn tich khi long at oc chinh xac cao, dang kt tua
phai thoa mn nhung yu cu sau:
- Kt tua cn phai thuc t khng tan, long nguyn t cn phn tich con lai trong
dung dch sau khi kt tua phai nho hn 0,1 mg tuc la khng vot qua nhay cua cn
phn tich. Mun vy khi tin hanh kt tua ta phai chn nhung iu kin thich hop nh pa
ti u, nng thuc thu, nhit thich hop kt tua hinh thanh thuc t khng tan.
- Kt tua thu oc cn phai tinh khit, khng cng kt, hp phu hay hp thu cac tap
cht. Nu co cht la ln vao thi no phai oc loai tru trong qua trinh lc, rua, sy, nung.
Chi co nh vy thi dang cn moi co thanh phn xac nh ung ung voi cng thuc hoa hc
cua no.
- Kt tua cn thu oc doi dang d lc rua co th tach ra khoi dung dch mt
cach nhanh chong va thun loi nht.
- Dang kt tua phai chuyn thanh dang cn d dang va hoan toan khi sy hoc nung.
2.3.2.2. u cu dang cn
Dang cn phai thoa mn cac yu cu sau:
- phai co thanh phn xac nh, ung voi cng thuc hoa hc xac nh.
- kha bn v mt hoa hc: trong khng khi no khng hut m, khng tac dung voi oxi
va khi cacbonic, khng b phn huy doi tac dung cua anh sang trong qua trinh lam ngui
va cn,...
- ham long cac nguyn t phn tich trong dang cn cang nho cang tt, tuc h s
chuyn chang nho cang tt, vi nh vy sai s mc phai khi phn tich (do cn, do kt tua
b tan khi rua, ..) s it tuc la kt qua phn tich cang chinh xac.
Thi du, co th xac nh Cr
3
doi dang cn la BaCrO
hoc Cr
2
O
3
. Gia su, sai s
tuyt i khi cn BaCrO
va Cr
2
O
3
u la 1 mg, nhng khi cn o dang Cr
2
O
3
thi sai s la
2 x 2/12 0,mg Cr, con khi cn o dang BaCrO
thi sai s la 2x1/23,3 0, 20mg Cr,

nho hn trong hop troc 0,/0,23, ln.
3.2.3. Cac iu kin kt tua hoan toan mt cht
Khi tin hanh kt tua mt ion nao o, ta phai tim nhung iu kin ti u chuyn
ion o vao dang kt tua hoan toan va kt tua tao thanh phai co kich thoc hat lon, it hp
phu cac cht bn, d lc, d rua, ...
- mun kt tua hoan toan mt cht ta thong dung long d thuc thu so voi long
tinh theo ly thuyt (tinh theo tich s tan), thong la d gp i hoc nhiu hn (vi tan
cua kt tua giam nhiu khi trong dung dch co mt ion chung).
2.3.3. Cac boc tin hanh va k thut phn tich trng long
2.3.3.1. K thut kt tua
a) chn thuc thu thich hop kt tua:
b) Chn iu kin kt tua:
2.3.3.2. Lc va rua tua
Gpc* co th lc qua phu xp hoc giy lc.
Giy lc:
Phu xp:
Doc anh s 1, 2, 3, ... s cang tng thi phu cang mn. Khi dung lu y bao quan
lop xp (tranh cao sat lam hong lop xp).
j/. kt tB.*
Muc ich cua vic rua kt tua la lam sach kt tua, nhng kt tua khng b tan mt
trong qua trinh rua. D thoa mn yu cu trn ta co th chn mt trong cac dung dch rua
sau tuy thuc vao loai kt tua:
-noc rua la dung dch co chua thuc thu: nu thuc thu d b phn huy hoac bay
hi khi sy va nung kt tua thi co th thm thuc thu vao noc rua, bng cach nay s lam
giam bot su tan kt tua.
- noc rua la dung dch in ly co th tranh oc hin tong pepti hoa cua cac kt
tua keo.
- dung dch rua co chua cht ngn can su thuy phn cua kt tua ngn can kt tua
tan.
Vi du kt tua MgNH
PO
d b thuy phn:
MgNH
PO
H
2
O

MgHPO
NH
OH
D ngn can phan ung nay ta dung dung dch rua co chua NH
3
rua kt tua
MgNH
PO
.
- nu kt tua it tan, khng b thuy phn, khng b pepti hoa khi lc thi chi cn rua
bng noc ct.
Di voi mi loai noc rua, khi rua cn nho rng voi cung mt long noc rua nn
chia ra rua lam nhiu ln va cn noc rua cua ln troc chay ht ri moi rua tip ln
sau, rua nh vy kt tua moi sach. Kt qua tinh toan cho thy:
2.3.3.3. Chun b dang cn
Sy kt tua: sau khi lc xong kt tua, ta ly mt to giy lc (ghi tn phn bit)
va dung ln phu ung kt tua ri m sy o nhit -10 C trong khoang 20-30
phut. Di voi loai kt tua chi cn sy chuyn sang dang cn thi cn phai sy nhiu ln
n khi kt tua co khi long khng i.
Nung kt tua:
Kt tua sau khi sy xong, ta ly kt tua cung giy bac ra khoi phu va a vao chen
nung (chen su hay platin theo yu cu) bit khi long chinh xac ri a vao lo nung,
moi u o ngoai ming lo ri moi dn dn chuyn vao trong lo tranh hin tong
nhit tng t ngt, giy lc chay manh lam bay ht cht kt tua va nu chen su thi d
b v. Nung khoang 1h thi ly chen ra, t trn tm amiang va cho vao binh hut m, cho
ngui ri m cn, ri lai m cn. Cu lam nh vy cho n khi khi long kt tua khng
i.
2.3.. Cach tinh toan trong phn tich trng long
2.3..1. H s chuyn (K)
Thng thong dang cn khng phai la dang cn xac nh ham long, vi vy, tu
khi long cua dang cn tinh khi long cua dang cn xac nh ham long. Do o,
tin cho vic tinh kt qua phn tich, ngoi ta a ra khai nim h s chuyn. Do la ai
long ma ta cn phai nhn khi long cua dang cn voi no oc khi long cua dang
cn xac nh, thng thong h s chuyn la ti s cua khi long cua mt, hai hoc nhiu
nguyn tu hoc phn tu hoc ion cua dang cn xac nh va khi long phn tu cua dang
cn. Noi cach khac h s chuyn chi ra co bao nhiu gam nguyn t (cht) cn nh phn
trong 1 gam dang cn. Trong trong hop cn xac nh Si thi h s chuyn tu SiO2 (dang
cn) thanh Si dang cn xac nh la:
c.n ,.ng
,nh Z.c c.n ,.ng
S
S
K
Thi du khac: nu dang cn la Mg

2
P
2
O
va dang cn xac nh ham long la Mg; MgO

hay MgCO
3
thi h s chuyn ln lot la:
2 2
2
I ` Sg
Sg
S
S
K
2 2
2
I ` Sg
SgI
S
S
K
2 2
3
2
I ` Sg
Sg5I
S
S
K
2.3..2. H s pha long (F)
2.3..3. Cng thuc tinh
Gia su long cn mu la a (g). Khi long dang cn la q (g). K la h s chuyn.
Ham long tinh theo khi long cua A la:
100
.
) (
.
K 2
" 5
Nu p gam mu chua trong V ml dung dch ma ly ra v ml phn tich thi:
100
.
. .
) (
1 .
P K 2
" 5
Trong trong hop phn tich khi va hi thi cach tinh kha n gian. Vi du, xac nh
m cua mu, ta ly p (g) mu, Sau khi sy kh thi con lai p` (g). Vy m cua mu
la:
100
,
p
p p
5
2.3.. Vi du nh long bng phng phap trng long
2.3..1. Dnh long ion Fe
3
Trong mi trong acid pH Fe
3
s phan ung voi dung dch NH
OH tao kt tua
Fe(OH)
3
. Kt tua oc rua trong dung dch nong chua NH
NO
3
(1). Lc, than hoa,
nung o nhit 0 C, thu oc dang cn Fe
2
O
3
, tu o tinh ham long cua Fe
3
trong
mu.
2Fe
3
NH
3
(x)H
2
O 2Fe(OH)
3
.xH
2
O NH
2Fe(OH)
3
.xH
2
O (00
0
C) Fe
2
O
3
(x3)H
2
O
2.3..2. Dnh long ion Al
3
- TK
2.3..3. Dnh long ion Mg
2

Trong mi trong kim nhe ammoniac, Mg
2
s phan ung voi dung dch
(NH
)
2
HPO
.H
2
O tao kt tua MgNH
PO
.H
2
O. Kt tua oc rua bng dung dch NH
3
10 cho n khi ht ion Cl
-
(thu bng AgNO
3
) ri rua tip trong dung dch nong chua
NH
NO
3
(1). Lc, than hoa, nung o nhit 0 C, thu oc dang cn Mg
2
P
2
O
, tu
o tinh ham long cua Mg
2
trong mu.
Mg
2
(NH
)
2
HPO
H
2
O MgNH
PO
.H
2
O NH
MgNH
PO
.H
2
O MgNH
PO
H
2
O
2MgNH
PO
Mg
2
P
2
O
2NH
3
H
2
O
2.3... Dnh long ion SO
2-
- TK
2.3... Dnh long ion PO
3-
- TK

Giáo Án Hóa Phân Tích

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Copyright:

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Giáo Án Hóa Phân Tích

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HA PHN TCH

Trong o K la hng s cn bng in li.

Nu C 0, 0 thi dung dch rt long, tng tac tinh in khng an k, I1.

acid 1 baz 2 baz 1 acid 2

). Mt cp acid baz lin hop oc biu din nh sau:

b hidrat hoa oc gi la ion hidrono hay oxoni.

Cp acid baz lin hop: CH

khng phai la acid, CN

thay i trong khoang 10M n 10

, tu o tinh pH cua dung dch cac h acid-baz

ta chia lam hai trong hop:

nn phai tinh n su phn li cua noc.

nn co th bo qua su phn li cua noc.

phai tinh ca su phn li

Pt bao toan khi long /v HA:

, nhng khng th bo qua H

khi khng tinh n su phn li cua noc:

- Pt bao toan khi long cua cac cu tu trong dung dch:

Thay vao cng thuc tinh OH

b) Baz khng qua yu, K

- Tinh gia tr gn ung cua H

Gia tr pH cua dung dch luc o s la :

co tinh acid v cung

Pt bao toan khi long cua CH

co ion trung tm Al va phi tu (ligand) H,

kali hexanitrocobaltnat ().

b) Dua vao du in tich cua ion phuc (cu ni)

- Phuc cation: LiAlH

- Phuc anion: Co(NH

Giua M va L co th co nhiu phuc ML

va ligand L (vi L la mt baz). Phan ung tao ra HL, H

va ligand L xay ra cang manh, phuc

va ligand L thi bn cua

la mt hng s gi la tich s tan cua AgCl va ki hiu bng T

Do chinh la mi lin h giua tan va tich s tan.

co kha nng phan ung voi B va

s xay ra phan ung oxi

, l thu hai cho dung dch

. Ni hai dung dch bng mt hinh chu ung dung dch

tng dn, nng ion Cu

. Ngoc lai , cac ion m SO

la 1M (pH 0). B mt in cuc hp thu khi hiro,

trong nua pin 2H

- Th in cuc chun cua cp M

trong nua pin 2H

(khi khng co anion

X H, thGng )hot)h.t .77oni.!E

2.1.3.2. Cac n v thong dung biu din kt qua phn tich

Vi du: Tu mui CuSO

, noc ct va cac dung cu cn thit, hy tinh toan va nu cach

co trong 0,0 mol CuSO

cho vao cc thuy tinh dung tich 0ml. D dn dn

Vi du: pha ch 100ml dung dch MgSO

0, M tu dung dch MgSO

cho vao cc thuy tinh 200ml. D tu tu noc ct vao

`h. ch ,ung ,@ch tq %u= rwn tnh th

2.1... Pha dung dch co nng phn trm khi long

Di voi cht rn ngm noc:

Pha dung dch co nng phn triu C

, noc ct va cac dung cu cn thit, hy tinh toan va nu cach pha

khan cho vao cc 100ml. Cn ly g noc ct, ri dn vao cc

/.1.[. qa ;> thGng 6W !(! 6?t ru8 thA! nghi,7

phan anh su sai lch giua kt qua o x