A.

M U
I. L do chn ti:
Hin nay trn th gii cuc cch mng khoa hc v cng ngh ngy cng din ra
mnh m v lm nn tng cho pht trin kinh t tri thc. Khoa hc cng ngh tr thnh
ng lc chnh ca s pht trin kinh t - x hi. S pht trin khoa hc cng ngh
lm i mi mnh m ni dung cng nh phng thc gio dc ca nhiu quc gia trn
th gii v Vit Nam l mt trong nhng nc .
Trc tnh hnh , ng ta ra ch trng pht trin gio dc vi quan im
Gio dc l quc sch hng u nhm mc tiu Nng cao dn tr, o to nhn lc,
bi dng nhn ti. Chnh v th m nhng nm gn y nn gio dc nc ta khng
ngng i mi, c bit l nhng mn khoa hc t nhin.
Ha hc l mt mn khoa hc thc nghim, n khng nhng cung cp nhng kin
thc c bn cho hc sinh m cn gip hc sinh ng dng trong nhiu lnh vc trong cuc
sng. V th i mi ni dung cng nh cch thc dy hc Ha hc l mt nhim v
quan trng trong quc sch pht trin gio dc hin nay. V vy, ti chn ti: Tm
hiu v phng php chun oxi ha kh v gii cc bi tp lin quan gp phn
b sung vo tng quan ti liu bi dng cho hc sinh gii cc trng THPT cc tnh,
nhm gip cc em c vn kin thc su hn v mng ha hc phn tch v t kt qu
cao trong cc k thi hc sinh.
II. Mc ch chn ti :
Thng qua nhng bi tp ha hc nng cao nhm trang b cho hc sinh kin thc, rn
luyn k nng gii bi tp tch cc ha nhn thc, pht trin t duy logic sng to,
pht trin cho hc sinh nng lc t hc v nng cao hng th hc tp.
III. Phng php nghin cu:
Da trn h thng kin thc l thuyt ha hc phn tch, su tm, bin son v phn
dng cc dng bi tp thng gp trong mng chun oxi ha kh ca b mn ha
hc phn tch.
1
B. NI DUNG
I.Khi qut v phng php chun oxi ha kh:
I.1. Phn loi phng php chun oxi ha kh:
Phng php chun oxi ha kh l phng php chun m trong phn
ng xy ra trong qu trnh chun l phn ng oxi ha kh, tc l phn ng c km
theo s trao i electron.
Trong thc t s phn ng oxi ha kh l rt nhiu nhng do tnh phc tp ca
phn ng oxi ha kh m s phn ng c s dng trong phn tch th tch l rt hn
ch. Bi v s dng trong phn tch th tch phi tha mn cc iu kin sau:
- Phn ng xy ra phi theo ng h s t lng.
- Tc phn ng xy phi nhanh.
- Phi c kh nng xc nh c im tng ng.
Mc d cc phn ng oxi ha kh chn trong phng php phn tch th tch phi
tha mn 3 iu kin trn nhng trong thc t phn ng oxi ha kh bao gi cng rt
phc tp v phn ng ph thuc vo nhiu yu t. V th trong qu trnh chun cn
phi nghin cu chn c cc iu kin ti u. Php chun oxi ha kh lin
quan n mt s cht kh v cht oxi ha c trng c dng lm dung dch chun v
ngi ta ly cc dung dch chun t tn cho cc phng php.
1. Phng php pemanganat:
Phng php ny da trn tc dng oxi ha ca dung dch KMnO
4
. Phng php
ny cho php xc nh c nhiu cht kh v c v hu c bng chun trc tip hoc
c th xc nh cc cht oxi ha bng phng php gin tip.
Phng php pemanganat thng khng cn ch th.
2. Phng php icromat:
Phng php ny dng dung dch K
2
Cr
2
O
7
lm dung dch tiu chun xc nh
cc cht kh v k c cht oxi ha. Ni chung phng php ny gn ging phng php
pemanganat nhng c mt s u im: dung dch tiu chun c th pha ch c t
lng cn chnh xc, dung dch sau khi pha ch bn theo thi gian, c th tin hnh chun
2
trong mi trng axit HCl trong khi khng th thc hin c i vi phng php
pemanganat. Nhc im ca phng php ny l do tnh oxi ha ca K
2
Cr
2
O
7
yu hn
KMnO
4
nn tc phn ng xy c phn chm hn v phi a ch th t ngoi vo.
3. Phng php Iot:
L phng php s dng dung dch I
2
( thc cht l I
3
-
) hoc dung dch I
-
tin
hnh chun trc tip hay gin tip cc cht kh v cht oxi ha. Trong phng php
ny c mt cht h tr quan trng l natri thiosunfat Na
2
S
2
O
3
, ch th dng trong phng
php ny l h tinh bt.
Ngoi 3 phng php nu trn cn c cc phng php khc nh: phng php
Xeri ( dng dung dch Ce(SO
4
) lm cht oxi ha); phng php Bromat, phng php
vanadat...
I.2. ng chun ca phng php oxi ha kh:
C th m t y qu trnh chun oxi ha kh bng ng cong chun .
ng chun ca phng php oxi ha kh biu din s ph thuc gia th in
cc ca dung dch vi th tch thuc th dng (E-V) hoc a s l biu din s ph
thuc ca th vo t s lng ca cc cht tham gia phn ng chun ( E- P).
Khi cho mt th tch xc nh dung dch chun ca cht oxi ha hoc kh vo dung
dch cn chun (cha cht kh hoc cht oxi ha) th xy ra phn ng oxi ha kh.
Phn ng ny lm thay i nng cc cht phn ng sao cho khi cn bng , th oxi ha
ca hai cp oxi ha kh tr nn bng nhau ti mi thi im ca ng cong. V
nguyn tc tnh th ti mi thi im chun c th s dng phng trnh Nec p
dng cho h oxi ha kh bt k tham gia phn ng chun .
OX
1
+ ne Kh
1

Kh
2
OX
2
+ me
( OX: vit tc cht oxi ha, Kh: vit tc cht kh)
Phn ng c th vit tng qut:
aOX
1
+ bKh
2
cKh
1
+ dOX
2
Nh vy trong qu trnh chun trong dung dch lun tn ti hai cp oxi ha kh
lin hp OX
1
/Kh
1
v OX
2
/Kh
2
. Vic xy dng ng cong chun trong phng php
oxi ha kh cng c chia thnh 3 vng:
- Vng trc im tng ng.
3
- im tng ng.
- Vng sau im tng ng.
Ngoi tr im u cha chun , trong dung dch ch tn ti mt cp oxi ha -
kh ca dung dch cn xc nh, cn mi thi im ca php chun trong dung dch
tn ti 2 cp oxi ha - kh: mt ca cht phn tch, mt ca thuc th.
Tuy nhin:
Trc im tng ng: Do nng cht phn tch cn d so vi nng ca
thuc th v cht phn tch cn d so vi nng ca thuc th, v vy cp oxi ha-kh
ca cht phn tch l cp in hot (tc l vic tnh th ti thi im ny da vo cp oxi
ha kh ca cht phn tch).
Ti thi im tng ng: khi m c nng ca thuc th v cht phn tch
u rt b, vic tnh th da vo s t hp cc biu thc tnh th cho c hai cp oxi ha-
kh ca thuc th v ca cht phn tch. Gi tr ny l gi tr l thuyt, bi v thi im
ny c hai cp u khng in hot v th y l th hn hp.
Sau im tng ng: Khi nng ca cht phn tch l v cng b v lc ny
cho d thuc th, do th in cc c tnh theo cp oxi ha kh ca thuc th.
Ty thuc vo h s t lng ca cc cht oxi ha kh trong phn ng chun
oxi ha kh m ngi ta chia php chun thnh 2 loi:
+ Php chun i xng.
+ Php chun bt i xng.
Ngoi ra trong phn ng qu trnh trao i electron c th din ra theo th t nn
php chun c th tin hnh tng nc.
I.3. Mt s phng php chun oxi ha kh:
I.3.1. Phng php pemanganat :
I.3.1.1. Tnh cht oxi ha ca pemanganat: l cht oxi ha mnh. Sn phm ca
s oxi ha ph thuc vo mi trng:
Trong mi trng axit mnh: Ion
4
MnO

b kh thnh ion Mn
2+
khng mu:
4
8 5 MnO H e
+
+ +

2
2
4 Mn H O
+
+ 2
4
0
/
( 1,51 )
MnO Mn
E V
+

Trong mi trng trung tnh (hoc axit hoc baz yu) ion
4
MnO

b kh thnh
ion Mn
4+
(MnO
2
):
4
4 2
3 2 MnO e H O

+ +
2
4 MnO OH

+
4 2
0
/
( 0, 588 )
MnO MnO
E V

Trong mi trng baz kim: ion
4
MnO

b kh thnh
2
4
MnO

:
4
1 MnO e

+
2
4
MnO

( 2
4 4
0
/
0, 564 )
MnO MnO
E V


Bi v trong phn ng kh ion
4
MnO

c kh nng trao i vi mt s lp
electron (n 5e) nn phn ng kh ion
4
MnO

thng din ra qua cc giai on trung

gian: Mn(VI), Mn(VI), Mn(II), Mn(III). Trong dng Mn(III) l cht oxi ha mnh nht
(
0
( )/ ( )
1, 51
Mn III Mn II
E V
) nhng trng thi ny khng bn. Nn phng php pemanganat
thng c nhiu qu trnh ph vi cc sn phm trung gian. Vi l do ny i vi
phng php pemanganat ngi ta phi chn cc iu kin ti u.
I.3.1.2. iu ch dung dch KMnO
4
:
Dung dch KMnO
4
c tinh khit c bn cao nhng dung dch long li c
bn thp.
Do KMnO
4
l cht oxi ha mnh nn qu trnh bo qun phi ht sc cn thn,
trnh bi bm, trnh nh sng c bit trnh s c mt ca Mn(II) v MnO
2
.
V nhng l do c dung dch KMnO
4
tiu chun cn phi i hi thc hin
thao tc nh sau:
Khng pha ch dung dch t lng cn chnh xc v ngay c KMnO
4
ni l
nguyn cht cng cha mt lng vt MnO
2
l cht xc tc cho qu trnh phn hy
4
MnO

. Mt khc trong nc bao gi cng c cc cht kh c th kh ion

4
MnO

thnh
MnO
2
.
Pha ch dung dch c nng gn ng i t lng cn bng cch ha tan
KMnO
4
v H
2
O, un si dung dch mt thi gian sau lm lnh v lc ht vt MnO
2
(bng phu thy tinh, hoc phu ct) ri bo qun dung dch trong bnh thy tinh mu
nu nt nhm.
Chun ha dung dch KMnO
4
bng cc cht gc: Na
2
C
2
O
4
, H
2
C
2
O
4
. 2H
2
O v
mt s cht khc. Thng ch th l lng d rt b KMnO
4
sau im

tng ng.
Qu trnh chun cn ch mt s nguyn nhn sau y dn n sai s:
S oxi ha cm ng ion
4
2
2
C O

bi khng kh:
5
4
2
2 2
2 C O O H
+
+ +
2 2 2
H O CO +
(Tuy nhin do H
2
O
2
cng l cht kh n s b
4
MnO

oxi ha nn cng tiu th mt s

ng lng gam
4
MnO

nh
4
2
2
C O

nu nh khng c s phn hy H
2
O
2
).
Dung dch H
2
C
2
O
4
b phn hy chm khi un nng:
H
2
C
2
O
4
CO
2
+ CO + H
2
O
S phn hy chm KMnO
4
xy ra khi un nng
S c mt ca HCl b oxi ha cm ng bi ion
4
MnO

.
II.3.1.3 Mt s ng dng:
Ni chung phng php pemanganat c dng nh lng cc cht kh, v
d:
+ nh lng Fe
2+
: Fe c trong t nhin thng tn ti dng Fe(III) hoc
Fe(II). Khi chuyn vo dung dch th st di dng Fe
3+
hoc Fe
2+
hoc c mt ng
thi Fe
3+
v Fe
2+
v vy phi kh Fe
3+
thnh Fe
2+
ri chun bng dung dch KMnO
4
.
2
4
5 8 Fe MnO H
+ +
+ +
3 2
2
5Fe Mn H O
+ +
+ +
kh Fe
3+
thnh Fe
2+
c th dng kim loi c bit thng dng SnCl
2
v
trong dung dch nng SnCl
2
kh hon ton Fe
3+
thnh Fe
2+
.
2 3
2 Sn Fe
+ +
+
4 2
2 Sn Fe
+ +
+
Cn phi dng d SnCl
2
kh hon ton Fe
3+
nn lng d SnCl
2
c
oxi ha bng HgCl
2
.
SnCl
2
+ 2HgCl
2
SnCl
4
+ Hg
2
Cl
2
Tuy nhin cn trnh dng d nhiu qu SnCl
2
v n c kh nng kh tip
Hg
2
Cl
2
thnh Hg kim loi l cht phn ng mnh vi
4
MnO

.
Trong phn ng chun Fe
2+
bng dung dch
4
MnO

ngi ta dng H
2
SO
4
v c mt hn hp bo v gm MnSO
4
+ H
2
SO
4
+ H
3
PO
4
.
+ nh lng H
2
O
2
: Trong dung dch H
2
O
2
kh
4
MnO

:
2 2 4
5 2 6 H O MnO H
+
+ +
2
2 2
2 5 8 Mn O H O
+
+ +
Phn ng xy ra cng c giai on cm ng tng t nh phn ng gia
4
MnO

v
4
2
2
C O

.
6
+ nh lng nitrit: ion
2
NO

khng tc dng vi
4
MnO

trong dung dch trung

tnh hoc kim. Ch trong dung dch axit, un nng n b oxi ha hon ton.
2 4
5 2 8 NO MnO H
+
+ +
2
3 2
5 2 3 NO Mn H O
+
+ +
Do trong mi trng axit c kh nng to axit HNO
2
d bay hi nn qu
trnh chun s thu c kt qu thp v vy php chun thng c tin hnh theo
hai cch sau y:
- Thm chnh xc dung dch
2
NO

t buret vo dung dch

4
MnO

c
axit ha cho ti khi mt mu dung dch KMnO
4
.
- Tt hn ht l cho d dung dch KMnO
4
vo dung dch nitrit v sau
chun lng d KMnO
4
bng phng php Iot.
I.3.2. Phng php icromat:
I.3.2.1. Dung dch K
2
Cr
2
O
7
: l cht oxi ha trong mi trng axit.
2
2 7
6 14 Cr O e H
+
+ +
3
2
2 7 Cr H O
+
+
0
( 1, 36 ) E V
Dung dch K
2
Cr
2
O
7
rt bn, phn ng chun c th tin hnh trong mi trng
axit: H
2
SO
4
, HClO
4
v HCl.
Ch th dng trong phng php icromat c th dng cc ch th oxi ha kh
nh: iphenylamin, iphenyl benziin, tt hn c l natri iphenyl sunfonat.
K
2
Cr
2
O
7
p ng y yu cu ca cht gc v vy c th pha ch dung dch tiu
chun i t lng cn chnh xc.
I.3.2.2 ng dng: quan trng nht l chun Fe(II)
Vic dng Fe(II) c nhiu thun li chng hn: khi cn chun cc cht oxi ha
th ngi ta cho lng d chnh xc Fe(II) sau chun ngc Fe(II) d bng
K
2
Cr
2
O
7
, cn nh lng cc cht oxi ha th cho mui Fe(II) d bng K
2
Cr
2
O
7
, cn
nh lng cc cht kh th cho mui Fe(III) d v sau chun vi Fe(II) to ra
bng dung dch K
2
Cr
2
O
7
. Hoc cht kh phn ng chm vi Fe(III) th c th thm d
lng K
2
Cr
2
O
7
ri chun ngc lng K
2
Cr
2
O
7
bng Fe(II).
u im ca phng php icromat l mc d phn ng c s trao i ln s e
-
nhng khng qua nhiu giai on v c bit l khng c s oxi ha cm ng vi ion Cl
-
nn phn ng c th tin hnh trong mi trng HCl.
I.3.3. Phng php It:
7
I.3.3.1. Tnh oxi ha kh ca It:
Iot l cht oxi ha yu v iodua l cht kh yu
2( )
2
r
I e +
2I

2
0
/2
( 0,5345 )
I I
E V

V vy I
2
c th oxi ha c cc cht kh trung bnh ( H
2
S, H
2
SO
3
, Sn(II),...) v
iodua c th kh c cc cht oxi ha trung bnh tr ln (Fe
3+
, H
2
O
2
, ...)
.
Phng php It c dng nh lng c cc cht oxi ha v cc cht kh.
- Cc cht kh c th c chun trc tip bng it hoc cho tc dng vi I
2
ly d v sau chun lng d it bng dung dch natri thiosunfat (Na
2
S
2
O
3
).
- Cc cht oxi ha c nh lng bng cch cho tc dng vi dung dch KI
d trong mi trng axit v sau chun lng it gii phng ra bng dung dch
Na
2
S
2
O
3
.
Nh vy, trong phng php it phn ng quan trng nht l phn ng gia it
v Na
2
S
2
O
3
:
2
2 2 3
2 I S O

+
2
4 6
2I S O

+
I.3.3.2. Cch tin hnh chun : Cc php tin hnh chun trc tip cn phi
iu ch dung dch tiu chun I
2
bng cch ha tan I
2
rn vi dung dch KI th I
2
tan do
to phc:
2 3
I I I

+
.
xc nh chun ca dung dch I
2
ngi ta tin hnh chun bng dung
dch Na
2
S
2
O
3
vi ch th h tinh bt. Php chun trc tip c dng nh lng cc
ct kh c th nh hn so vi th ca
2
0
/2 I I
E
.
Chun gin tip: V hu ht cc phn ng gia I
2
vi cc cht kh xy ra
chm nn phi tin hnh chun gin tip hay chun ngc.
Nguyn tc:
Kh
1
+ I
2
( chnh xc) Ox
1
+ 2I
-
(1)

2
2( ) 2 3
2
du
I S O

+
2
4 6
2I S O

+
Hoc: Ox
1
+ 2I
-
(d) Kh
1
+ I
2
(2)

2
2( ) 2 3
2
taora
I S O

+
2
4 6
2I S O

+
I.3.3.3. Cc ngun gy sai s khi chun it:
* S oxi ha I
-
bi oxi khng kh:
8
4I
-
+ O
2
+ 4H
+
2I
2
+ 2H
2
O
S mt mt I
2
do s thng hoa, c bit nhit cao v th cn chun
nhit thp.
Phn ng xy ra trong mi trng axit yu hay baz yu bi v nu trong mi
trng axit mnh xy ra:
2
2 3
S O H
+
+
2 3
HS O

2 3
HS O

3
HSO S

+
Cn trong mi trng baz mnh:
I
2
+ OH
-
HOI + I
-
V nu c kim d:
HIO + OH
-
H
2
O + OI
-
- Do ch th h tinh bt to phc vi I
2
kh bn nn mt lng I
2
ng k tn ti
dng phc vi ch th iu ny s gy nn sai s nn ngi ta ch cho h tinh bt khi
chun gn n im tng ng.
I.3.3.4. ng dng ca phng php It:
* nh lng cht kh: v d nh lng asen. Phng php ny da trn vic
chun dung dch asen (III) bng it ch th h tinh bt. Phn ng tin hnh trong mi
trng pH t 4 -9 thng dng NaHCO
3
.
3 3 3
4 H AsO I OH

+ +
2
4 2
3 3 HAsO I H O

+ +
* nh lut cht oxi ha: Chng hn nh lng Cu
2+
: cho Cu
2+
phn ng vi I
-
d
phn ng xy ra thnh I
2
v sau chun I
2
bng sung dch Na
2
S
2
O
3
. Phn ng xy ra:

2 x Cu
2+
+ 1e Cu
+
2I
-
I
2
+ 2e
2 x Cu
+
+ I
-
CuI
I
2
+ I
-

3
I

2Cu
2+
+ 5I
-

3
I

+ 2CuI K = 10
10,7
.
Hng s cn bng ln, phn ng thc t xy ra hon ton. Mt s yu t nh
hng n phn ng:
9
- axit yu: Nu pH > 4 th Cu
2+
c kh nng to phc hiroxo, phn ng xy ra
chm, im cui chun khng r, nu pH < 0,5 th xy ra s oxi ha r rt ion I
-
bi
oxi khng kh. iu kin pH ti u l 3.
- Kt ta CuI c kh nng hp th I
2
trn b mt, lm cho php phn ng ca I
2
vi
Na
2
S
2
O
3
kh khn v lm kt ta c mu thm kh xc nh im tng ng. hn
ch kh nng hp th ca CuI ngi ta cho thm KSCN vo dung dch chun .
II. Ni dung bi tp:
II.1. Bi tp chun bng phng php pemanganat:
Bi gii:
Phn ng chun :
5 X Fe
2+
Fe
3+
+ e

4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
Ti im tng ng:
p dng L ng lng ta c:
2
4
Fe MnO
S S
+

2 2
4 4
( ) ( ) ( ) ( ) N Fe Fe N MnO MnO
C V C V
+ +

0,01.50=0,01.5.
4
( ) MnO
V

4
( ) MnO
V

=
0, 01.50
0, 01.5
=10(ml)
10
BI 1: Chun 50ml dung dch FeSO
4
0,01M bng dung dch KMnO
4
0,01M
pH=0. Hy tnh gi tr l thuyt ca th in cc trong dung dch chun khi cho cc
th tch dung dch KMnO
4
theo cc s liu sau:
a, 9,5ml
b, 10ml
c, 10,5ml
Cho: 2
4
0
/ MnO Mn
E
+ = 1,51V; 3 2
0
/ Fe Fe
E
+ + = 0,77V [1]
a, Th tch dd KMnO
4
dng chun l 9,5ml tc l chun dng trc
im tng ng, ta c:

t
t
9, 5 10
% 100% 5%
10
c

V V
q
V


Trc im tng ng:
Khi trong dung dch ang d Fe
2+
nn th ti thi im ny c tnh da vo
cp ca st.Theo phng trnh Nec ta c:
E
t
= 3 2
0
Fe / Fe
E
+ + +
3
2
0, 059
log
1
Fe
Fe
+
+
1
]
1
]
2
Fe
+
1
]
=
0 0
0
5
i
i
C V CV
V V

+
v
3
0
5
i
i
CV
Fe
V V
+
1
]
+
E
t
= 3 2
0
Fe / Fe
E
+ + +
0 0
5 0, 059
log
1 5
i
i
CV
C V CV
0 0
5
v
i
CV
P
C V

Nn chia t v mu ca biu thc di log cho C

0
V
0
, ta c:
E
t
= 3 2
0
Fe / Fe
E
+ + +
0, 059log
1
P
P
Thay q = P-1 ta c :
E
t
= 3 2
0
Fe / Fe
E
+ + +
1
0, 059log
q
q
+

(1)
( )
5
Thay q 5% v o 1
100

5
1
100
0, 77 0, 059log 0,845
5
100
t
E V

+
+
b, Th tch dd KMnO
4
dng chun l 10ml tc l chun dng im tng
ng
Ti im tng ng:
Th c tnh da vo hn hp ca 2 cp:
11
3 2
2
4
3 2 2
4
3
0
2 /
8
4
0
2 /
8
3
4
0 0
2 2 / /
E 0, 059log
.
5E 5 0, 059log
. .
6E = 5 0, 059log
.
td
Fe Fe
td
MnO Mn
td
Fe Fe MnO Mn
Fe
E
Fe
MnO H
E
Mn
Fe MnO H
E E
Fe Mn
+ +
+
+ + +
+
+
+
+
+ +
+ +
1
]
+
1
]
1 1
] ]
+
1
]
1 1 1
] ] ]
+ +
1 1
] ]
Ti im tng ng:
2
4
5 Fe MnO
+
1 1
] ]
v
3 2
5 Fe Mn
+ +
1 1
] ]
Tnh theo
3
Fe
+
1
]
ta c:
3 2 2
4
8
3
4
0 0
t
3 / /
4
. .
6E = 5 0, 059log
5 .
5

Fe Fe MnO Mn
Fe MnO H
E E
Fe
MnO
+ + +
+ +
+

1 1 1
] ] ]
+ +
1
]
1
]
3 2 2
4
8
0 0
t
3 / /
6E = 5 0, 059log

Fe Fe MnO Mn
H
E E
Fe
+ + +
+
+
1
]
+ +
1
]
3 2 2
4
0 0
/ / 3
t
5
0, 059 0, 059
E = .8log log
6 6 6
Fe Fe MnO Mn

E E
H Fe
+ + +
+ +
+
1 1 +
] ]

3 2 2
0 0
3 / /
t
5
0, 059
E = 0, 0787 log
6 6
Fe Fe MnO Mn

E E
pH Fe
+ + +
+
+
1
]
(2)
Tuy nhin do ti im tng ng gi tr sau cng trong biu thc (2) khng ln so
vi gi tr u nn ta c biu thc cui cng l:
3 2 2
4
0 0
/ /
t
5
E = 0, 0787
6
Fe Fe MnO Mn

E E
pH
+ + +
+

V pH=0 nn:

3 2 2 2
4
0 0
/ /
t
5
0.77 5.1, 51
E = 1, 387
6 6
Fe Fe MnO Mn

E E
+ + +
+
+

V
c) Th tch dd KMnO
4
dng chun l 10,5ml tc l chun dng thi im
sau im tng ng:

10, 5 10
% 100% 5%
10
c td
td
V V
q
V



12
Sau im tng ng:
Lc cho d dung dch MnO
4
-
nn th ti thi im ny c tnh da vo cp oxh-kh
ca mangan.
2
4
8
4
0
2 /
0, 059
log
5
c
MnO Mn
MnO H
E E
Mn
+
+
+
1 1
] ]
+
1
]
(3)
Vi:
0 0 0 0
4
0 0 0
5
5( ) 5( )
i i
i i i
CV C V CV C V
MnO
V V V V V V

1
]
+ + +
v
2 0 0
0
5( )
i
C V
Mn
V V
+
1
]
+
Thay
4
MnO

1
]
v
2
Mn
+
1
]
vo (3)
2
4
0 0 0 0
/
0 0 0
8.0, 059 0, 059 5 5( )
(3) log log .
5 5 5( )
i i
c
MnO Mn
i
CV C V V V
E E H
V V C V
+
+
+
1 + +
]
+
2
4
0 0 0
/
0 0
8.0, 059 0, 059 5
log log
5 5
i
c
MnO Mn
CV C V
E E H
C V
+
+

1 + +
]
Mt khc chia c t v mu ca biu thc
0 0
0 0
5
i
CV C V
C V

cho C
0
V
0
(lu : P=
0 0
5
i
CV
C V
) v chuyn q=P-1 thi biu thc sau cng l:
2
4
0
/
8.0, 059 0, 059
log log
5 5
c
MnO Mn
E E H q
+
+
1 + +
]
V pH=0 nn: 2
4
0
/
0, 059
log
5
c
MnO Mn
E E q
+
+
(4)
5
Thay q 5%
100

vo (4)
0, 059 5
(4) 1, 51 log 1, 495
5 100
c
E +
V.
Hay: E
C
= 1,495V.

13
VO
2
+
, ,
BI 2: Mt mu phn tch cn nng 0,225g gm Fe v Fe
2
O
3
c ha tan trong
dung dch v Fe(III) c kh thnh Fe(II). Sau chun bng dung dch KMnO
4
th ht 37,5ml KMnO
4
0,0991N. Tnh hm lng % ca Fe v Fe
2
O
3
trong mu phn
tch. [1]
Bi gii:
Gi khi lng ca Fe v Fe
2
O
3
trong mu ln lt l: a(g) v b(g).
Suy ra: a + b = 0,225 (1)
Phng trnh chun :
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
p dng quy tc ng lng:
2
4
Fe MnO
S S
+

2
4
'
( ) ( )
. .
N Fe N MnO
V C V C
+

4
2
'
( ) 3
.
37,5.0, 0991
3, 72.10 ( )
1000 1000
N MnO
Fe
V C
n mol

Ta li c:
Fe
3+
+ e Fe
2+
b/80 b/80
Suy ra: a/56 + b/80 = 3,72.10
-3
. (2)
T (1) v (2), ta c: a = 0,0556(g)
b = 0,1694(g)
Vy: %Fe = (0,0556/0,225) . 100% = 24,71%
%Fe
2
O
3
= (0,1694/0,225) . 100% = 75,29%.
14
VO
2
+
, ,
BI 3: 0,1 g mu phn tch cha V, Cr, Mn c phn hy thnh dung dch . Sau
khi ch ha dung dch cc nguyn t tn ti di dng VO
2
+
, Cr
2
O
7
2-
,
4
MnO

. Chun
dung dch bng dung dch chun Fe
2+
0,1 M ch ht 50 ml . Ion VO
2+
to thnh c
chun bng dung dch chun KMnO
4
0,01M th ht 5ml . Sau thm vo lng
mui pitphtphat to phc vi Mn(III) khi chun Mn
2+
bng dung dch KMnO
4
trn , th tch tiu tn ln chun ny l 10ml . Tnh hm lng % mi kim loi trong
mu.
( V=50,49 ; Cr =52 ; Mn=54,94 ). Bit E
0
Fe
3+
/Fe
2+
= 0,77V ; E
0

VO2
+
/VO
2+
=1 V ;
E
0

Cr2O7
2-
/
2Cr
3+
= 1,36V ; E
0

MnO4
-
/


Mn
2+
= 1,51V. [1]
Bi gii : Tm tt s chun nh sau:






Trong mu phn tch cha V, Cr , Mn
Sau khi ch ho ta c dung dch gm:
2
2
VO

,
2
7 2
O Cr ,

4
MnO .
* Chun dung dch bng dung dch tiu chun Fe
2+
0,1M ht 50ml.
Ta c: + + 2 3
/ Fe Fe
o
E
= 0,771(V)
+ 3 2
7 2
2 / Cr O Cr
o
E = 1,33 (V)

+ + 2
2
/VO VO
o
E = 1 (V)
+ 2
4
/ Mn MnO
o
E = 1,51 (V)
Vy th t phn ng chun xy ra l:
+ u tin Fe
2+
kh

4
MnO thnh Mn
2+
:
5 x Fe
2+
Fe
3+
+ e
4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O (1)
+ Sau : Fe
2+
kh
2
2 7
Cr O

thnh Cr
3+
:
6 x Fe
2+
Fe
3+
+ e
2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
6Fe
2+
+
2
2 7
Cr O

+ 14H
+
2Cr
3+
+6Fe
3+
+ 7H
2
O
15
V, Cr, Mn
VO
2
+
, ,
Ch ha
Fe
2+
VO
2+
, Cr
3+
, Mn
2+
VO
2
+
, Cr
3+
Mn
2+
VO
2
+
, Cr
3+
, Mn
3+

4
MnO

4
MnO
+ Cui cng Fe
2+
kh
+
2
VO thnh VO
2+
:
Fe
2+
Fe
3+
+ e
2
VO
+
+ 2H
+
+ e VO
2+
+ H
2
O
Fe
2+
+
2
VO
+

+ 2H
+
Fe
3+
+ VO
2+
+ H
2
O
Vy, ta c:
S lg
+
2
VO + S lg
2
7 2
O Cr + S lg

4
MnO = S lg Fe
2+

+
2
VO
S
+
2
7 2
O Cr
S
+

4
MnO
S
=
+ 2
Fe
S (*).
Gi x, y, z ln lt l s ng lng gam ca V, Cr v Mn trong mu phn tch ban
u.
Sau khi ch ho ta c dung dch gm:
2
2
VO

,
2
7 2
O Cr ,

4
MnO .
Ta c :
+
2
VO
S
= S
V
= x
2
7 2
O Cr
S
= 3 S
Cr
= 3y

4
MnO
S
= 5 S
Mn
= 5z
+ 2
Fe
S =
0,1.50
1000
= 5.10
-3
Thay vo (*) ta c : x + 3y + 5z = = 5.10
-3
(**)
* Sau chun ion VO
2+
to thnh bng dung dch chun KMnO
4
0,01M ht
5ml.
5 x VO
2+
+ H
2
O
2
VO
+

+ 2H
+
+ e
4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5VO
2+
+ H
2
O +
4
MnO

Mn
2+
+ 5
2
VO
+

+ 2H
+
(2)
Ta c:
+ 2
VO
S
=

4
MnO
S
= = 2,5.10
-4
= x (***)
* Mt khc qu trnh chun VO
2+
bng dung dch chun KMnO
4
to ra Mn
2+
.
Vy Mn
2+
trong dung dch lc ny c to ra t phng trnh (1) v (2).
+ (1) : 2
Mn
S
+ to ra = S
Mn
ban u = z.
16
PbC
2
O
4

H
2
C
2
O
4

+ (2) : S
Mn
2+
to ra =
5
1

4
MnO
S
chun =
5
1
= 5. 10
-5
Vy tng s ng lng ca Mn
2+
trong dung dch lc ny l: S
Mn
2+
= z + 5. 10
-5
* Chun Mn
2+
bng dung dch chun KMnO
4
0,01M ht 10ml:
4 x Mn
2+
Mn
3+
+ e

4
MnO

+ 8H
+
+ 4e Mn
3+
+ 4H
2
O
4Mn
2+
+
4
MnO

+ 8H
+
4Mn
3+
+ 4H
2
O
Ta c:
S
Mn
2+
=

4
MnO
S
Hay : z + 5. 10
-5
=
4.0, 01.10
1000
= 4.10
-4
z = 3,5 .10
-4
(****)
T (**) ; (***) ;(****) ta c h sau :
x + 3y + 5z = 5.10
-3
x = 2,5 . 10
-4
y = 10
-3
z = 3,5 .10
-4
Vy:
+ S
V
= x = 2,5.10
-4

Khi lng ca V l : m
V
= S
V
.
V
= 2,5. 10
-4
50,94 = 0,0127 (g )
Phn trm ca V l : %V =
0, 0127.100
0,1
= 12,7 %
+ S
Cr
= y = 10
-3

Khi lng ca Cr l : m
Cr
= S
Cr
.
Cr
= 10
-3
= 0,052 (g)
Phn trm ca Cr l : %Cr =
0, 052.100
0,1
= 52 %
+ S
Mn
= z = 3,5.10
-4

Khi lng ca Mn l : m
Mn
= S
Mn
.
Mn
= 3,5.10
-4
. 54,94 = 0,0192(g )
Phn trm ca Mn l : %Mn =
0, 0192.100
0,1
= 19,2% (: ng lng gam )
17
PbC
2
O
4

H
2
C
2
O
4

BI 4: 1,234 g cht phn tch cha PbO v PbO
2
c ch ha vi 20ml
H
2
C
2
O
4
0,25 M kh PbO
2
thnh Pb
2+
. Sau dung dch c trung ha bng NH
3
kt ta ton b ch di dng xalat ch . Chun nc lc thu c bng dung
dch KMnO
4
0,04M th ht 10ml. Ho tan kt ta trong axit v chun dung dch
bng dung dch KMnO
4
0,04M ht 30 ml. Hy tnh thnh phn % ca PbO v PbO
2
trong mu phn tch ? [2]
Bi gii : Tm tt qu trnh phn tch mu:










Gi s ng lng gam ca PbO v PbO
2
ln lt l x v y
Ch ho hn hp bng dung dch H
2
C
2
O
4
. Khi cho H
2
C
2
O
4
vo th:
* Mt phn H
2
C
2
O
4
dng ho tan PbO, sau to kt ta PbC
2
O
4
PbO + H
2
C
2
O
4
PbC
2
O
4
+ H
2
O (1)
Gi S
1
l s ng lng gam ca H
2
C
2
O
4
dng trong phn ng (1).
Vy ta c: x = S
1

18
PbO, PbO
2
Pb
2+
, PbC
2
O
4
H
2
C
2
O
4
H
2
C
2
O
4
PbC
2
O
4

H
2
C
2
O
4
d
CO
2
, H
2
O H
2
C
2
O
4

CO
2
, H
2
O
Axit ho
KMnO
4
KMnO
4
* Mt phn dng kh PbO
2
thnh Pb
2+
:
2 x H
2
C
2
O
4
2H
+
+ C
2
O
4
2-
PbO
2
+ 4H
+
+ 2e Pb
2+
+ 2 H
2
O
C
2
O
4
2-
2CO
2
+ 2e
PbO
2
+ 2H
2
C
2
O
4
Pb
2+
+ 2CO
2
+ 2 H
2
O + C
2
O
4
2-
(2)
Gi S
2
l s ng lng gam ca H
2
C
2
O
4
dng trong phn ng (2).
Suy ra: y = S
2

* Mt phn H
2
C
2
O
4
dng to kt ta PbC
2
O
4
vi Pb
2+
phn ng (2)
Pb
2+
+ C
2
O
4
2-
PbC
2
O
4
(3)
Ta c + 2
Pb
S
to ra phn ng (2) =
2
PbO
S
= y.
Gi S
3
l s ng lng gam ca H
2
C
2
O
4
dng trong phn ng (3)
Ta c: y = S
3
hay S
2
= S
3
.
* Phn H
2
C
2
O
4
cn d l phn nc lc thu c, c chun bng dung dch
KMnO
4
0,04M ht 10ml:
5x H
2
C
2
O
4
2H
+
+ C
2
O
4
2-

2 x
4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5 x C
2
O
4
2-
2CO
2
+ 2e
5H
2
C
2
O
4
+ 2
4
MnO

+ 6H
+
2Mn
2+
+ 10CO
2
+ 8H
2
O (4)
Gi S
4
l ng lng gam ca H
2
C
2
O
4
cn d trong dung dch.
Ta c: S
4
=
4
KMnO
S
= = 2.10
-3

* Phn kt ta PbC
2
O
4
thu c l phn ng (1) v (3). Ho tan kt ta trong
axit:
PbC
2
O
4

+ H
+
Pb
2+
+ H
2
C
2
O
4
(5)
V vy :
4 2 2
O C H
S
(5) = S
1
+ S
3

* Chun dung dch thu c bng dung dch KMnO
4
0,04M ht 30 ml. Tc l
chun lng H
2
C
2
O
4
to thnh:
5H
2
C
2
O
4
+ 2MnO
4
-
+ 6H
+
2Mn
2+
+ 10CO
2
+ 8H
2
O
19
Ta c:
4 2 2
O C H
S
=
4
KMnO
S
Hay : S
1
+ S
3
=
0, 04.5.30
1000
= 6.10
-3
* Mt khc : tng s ng lng gam ca H
2
C
2
O
4

l:
S = S
1
+ S
2
+ S
3
+ S
4
=
0, 2.0, 25.20
1000
= 0,01
Suy ra:
S
1
+ S
2
+ S
3
+ S
4
= 0,01 S
1
= 4.10
-3
= x
S
2
= S
3
S
2
= 2.10
-3
= y
S
4
= 2.10
-3
S
3
= 2.10
-3
S
1
+ S
3
= 6.10
-3
S
4
= 2.10
-3
Vy :
S
PbO
= S
1
= 4.10
-3
= x
Khi lng ca PbO l : m
PbO
= S
PbO
.
PbO

= 4.10
-3
.
2
223
= 0,446 (g)
Phn trm ca PbO trong mu phn tch:
%PbO =
0, 446.100%
36,14%
1, 234

2
PbO
S

= S
2
= 2.10
-3
= y
Khi lng ca PbO
2
l : m
PbO2
=
2
PbO
S
.
= 2.10
-3
.
2
239
= 0,239 (g)
Phn trm ca PbO
2
trong mu phn tch l :
%PbO
2
=
0, 239.100%
19, 37%
1, 234


BI 5 : xc nh chun ca KOH v KMnO
4
ngi ta dng kalittraxalat
(KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O) lm cht u. Nng dung dch KOH xc nh c l
0,09963 N v ca KMnO
4
l 0,1328 N . Bit rng trong c hai trng hp trong c hai
trng hp th tch ca cc dung dch KOH v KMnO
4
ly chun u bng
50ml .Hy tnh s gam oxalat tiu th trong phn ng trn? [2]
20
Bi gii:
* Xt trng hp chun ca KOH :
3 KOH + KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O K
2
C
2
O
4
.K
2
C
2
O
4
.2H
2
O + 3 H
2
O (1)
ng lng ca KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O l : =
254
3
= 84,667
Ta c :
S lg KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O (1) = S lg KOH

2 4 2 2 4 2
KHC O .H C O .2H O KOH
S S

KOH KOH
m C .V
1000

=
0, 09963.50
1000
= 4,9815.10
-3
Vy, khi lng ca KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O tham gia khi chun KOH l :
m
1
= 4,9815.10
-3
84,667 = 0,4218 (g).
* Xt trng hp chun ca KMnO
4
:
5 x H
2
C
2
O
4
2H
+
+ C
2
O
4
2-

2 x
4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5 x C
2
O
4
2-
2CO
2
+2e
5H
2
C
2
O
4
+ 2
4
MnO

+ 6H
+
2Mn
2+
+ 10CO
2
+ 8H
2
O (2)
Ta c :
2
4 2 4
MnO C O
S S

2
4 4 2 4
2
2 4
N(MnO ) MnO C O
C O
C .V m
1000

4 4 2 4 2 2 4 2
2 4 2 2 4 2
MnO MnO KHC O .H C O .2H O
KHC O .H C O .2H O
C .5.V
2.m .2
1000 M



2 4 2 2 4 2
4 4
2 4 2 2 4 2
KHC O .H C O .2H O
MnO MnO
KHC O .H C O .2H O
C .5.V .
m
1000.4
M



2 4 2 2 4 2
KHC O .H C O .2H O
0,1328.50.254
m 0, 4216( )
1000.4
g
Khi lng ca KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O tham gia khi chun KMnO
4
l :
m
2
= 0,4216(g).
Vy : Khi lng ca KHC
2
O
4
.H
2
C
2
O
4
.2H
2
O tiu th trong cc qu trnh chun
trn l :
21
2 4 2 2 4 2
KHC O .H C O .2H O
m
= m
1
+ m
2
= 0,4218 + 0,4316 = 0,8434 (g).
B I 6 : Trn 100ml dung dch K
2
Cr
2
O
7
(10g K
2
Cr
2
O
7
trong 1 lt dung dch) vi
5ml H
2
SO
4
6N v 75ml dung dch FeSO
4
(80g FeSO
4
.7H
2
O trong 1 lt ). Chun hn
hp thu c vi dung dch KMnO
4
0,2121N th phi dng ht bao nhiu ml dung
dch ny? [2]
Bi gii:
Ta c cc phng trnh xy ra trong dung dch:
6 x Fe
2+
Fe
3+
+ e
2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
6Fe
2+
+
2
2 7
Cr O

+ 14H
+
2Cr
3+
+ 6Fe
3+
+ 7H
2
O

5 x

Fe
2+
Fe
3+
+ e

4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
Ta c:
( )
2 2 7
4
M(K Cr O )
M FeSO
10
C 0, 034( )
. 1.294
80
C 0, 288( )
. 1.278
m
M
V M
m
M
V M


p dng quy tc ng lng, ta c:
+ S lg ca
2 7
Cr O

= s lg
2
Fe
+

2
2 7
Cr O Fe
S S
+

2 2
2 7 2 7
N(Cr O ) Cr O N(Fe ) Fe
C . V C . V

1000 1000
+ +


2 2
2 7 2 7
M(Cr O ) Cr O M(Fe ) Fe
6.C . V C . V

1000 1000
+ +

2 7 2 7
2
2
M(Cr O ) Cr O
Fe
M(Fe )
6.C . V
6.0, 034.100
V =
C 0, 288

+
+

= 70,92 ml.
+ S lg ca
4
MnO

= s lg ca Fe
2+
d, ta c:

2
4
MnO Fe
S S
+

22
2 2
4 4
'
N(MnO ) MnO N(Fe ) Fe
C . V C . V

1000 1000
+ +


2 2
4
4
'
M(Fe ) Fe
MnO
N(MnO )
C . V
0, 288.(75 70,92)
V 5, 54( )
C 0.2121
ml
+ +

Vy, cn dng 5,54ml dung dch KMnO
4
chun ht hn hp sau phn ng.
BI 7: un nng 1g oxit st vi K
2
Cr
2
O
7
v ha tan cht chy trong axit. Kh
Fe
3+
bng SnCl
2
v thm HgCl
2
oxi ha ht SnCl
2
d. Chun hn hp thu c
vi dung dch KMnO
4
0,25N th ht 50ml KMnO
4
. Hy tm cng thc phn t ca oxit
st? [1]
Bi gii:
t cng thc chung ca oxit st l Fe
x
O
y
.
Ta c dy chuyn ha sau:

1
56 16 x y +

1
56 16 x y +
.x
1
56 16 x y +
.x(mol)
p dng quy tc ng lng:
S lg ca Fe
2+
= s lg ca
4
MnO

2
4
2 2
4 4
2 2
2
(
) ( )
( )
. .
1000 1000
.
50.0, 25
0, 0125( )
1000 1000
Fe MnO
N
MnO MnO Fe N Fe
Fe M Fe
Fe
S S
V C V C
V C
n mol
+
+ +
+ +
+

1
. 0, 0125
56 16
2
0, 3. 0, 2.
3
x
x y
x
x y
y

+

Vy chn x = 2 v y = 3, vy cng thc phn t ca oxit st l: Fe
2
O
3
.
23
2 2 7 2 4
3 2 3 K Cr O SnCl KMnO
x y
Fe O xFe xFe xFe
+ + +

BI 8: Ha tan 0,500g mt mu x cha st dng FeO v Fe
2
O
3
trong HCl.
Kh Fe
3+
thnh Fe
2+
, chun Fe
2+
ht 28,60ml KMnO
4
0,01120M. Mt khc, ha tan
0,750g mu x trong HCl trong bu kh quyn nit (trnh oxi ha Fe
2+
), ri chun
ngay Fe
2+
c trong dung dch ht 15,60ml KMnO
4
0,01120M.
a, Tnh tng hm lng % st c trong x?
b, Tnh hm lng % FeO v Fe
2
O
3
c trong x? [2]
Bi gii:
Th nghim 1: 0,500 g x cha FeO: a(g)
HCl
Fe
2+
chun hn hp ht
Fe
2
O
3
: b(g) Fe
3+
Fe
2+
28,60ml KMnO
4
0,01120M.

Phng trnh chun :
5 x Fe
2+
Fe
3+
+ e

4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
p dng quy tc ng lng:
S lg ca Fe
2+
= s lg ca
4
MnO

2
4
Fe MnO
S S
+

2 3
4
Fe Fe MnO
S S S
+ +
+

4 4 4 4
2 3
MnO N(MnO ) MnO M(MnO )
FeO Fe O
V .C V .5.C
S 2.S
1000 1000

+
3
a 2.b 28, 60.5.0, 01120
1, 6016.10
72 160 1000

+
(1)
Th nghim 2: 0,750 g x cha FeO: c(g)
HCl
Fe
2+ .
Chun hn hp ht
Fe
2
O
3
: d(g) Fe
3+

15,60ml dung dch KMnO
4
0,01120M.

Phng trnh chun :
24
5 x Fe
2+
Fe
3+
+ e

4
MnO

+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
5Fe
2+
+
4
MnO

+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
p dng quy tc ng lng:
S lg ca Fe
2+
= s lg ca
4
MnO

4 4
2
4
MnO N(MnO )
Fe MnO
V . C
S S
1000

+

4 4
2
MnO M(MnO )
FeO
Fe
V . 5.C
S = S
1000

+

4
c 5 . 0, 01120. 15, 6
8, 736. 10
72 1000
c 0, 063( ) g

Suy ra:
0, 063.100%
% FeO 8,39%
0, 750

Mt khc:
a.100%
% FeO 8,39%
0, 500


8,39%.0, 500
a 0, 042( )
100%
g
thay vo (1), ta c:
(1)
3
0, 042 2.b
1, 6016.10
72 160

+
b = 5,1.10
-4
(g).
Vy :
a, Tng hm lng st c trong x l :
2 3
Fe O
FeO
2.m
m 100%
% Fe ( .56 .56) .
72 160 0,500
+
-4
0, 042 2.5,1.10 100%
% Fe ( .56 .56) . 6, 6%
72 160 0,500
+
b, Hm lng FeO v Fe
2
O
3
c trong x l:
0,042.100%
% FeO 8,39%
0, 500

4
2 3
b.100% 5,1.10 .100%
% Fe O = 0,102%
0, 500 0, 500

25
BI 9: Ch ha 0,2630g qung pirolusit MnO
2
vi 0,3525g Na
2
C
2
O
4
nguyn cht
trong mi trng axit sunfuric 2N. Sau khi phn ng xy ra hon ton phi dng
30,50ml KMnO
4
0,01080M chun lng axit oxalic d. Tnh hm lng % ca
MnO
2
trong qung? [2]
Bi gii:
Ta c: ( )
2 2 4
3
Na C O
0, 3525
n 2, 63.10 mol
134


Qu trnh ch ha hn hp qung pirolusit MnO
2
v Na
2
C
2
O
4
bng axit sunfuric 2N xy
ra nh sau:
Na
2
C
2
O
4
+ H
2
SO
4
H
2
C
2
O
4
+ Na
2
SO
4
2,63.10
-3
2,63.10
-3
(mol)
2
2 4
C O

2CO
2
+ 2e
MnO
2
+ 2e + 4H
+
Mn
2+
+ 2H
2
O
MnO
2
+
2
2 4
C O

+ 4H
+
Mn
2+
+ 2H
2
O + 2CO
2
(1)
Sau khi ch ha, chun axit oxalic d bng dung dch KMnO
4
, p dng quy tc ng
lng, ta c:
Phng trnh chun :
5 x
2
2 4
C O

2CO
2
+ 2e
2 x
4
MnO

+ 5e + 8H
+
Mn
2+
+ 4H
2
O
5
2
2 4
C O

+ 2
4
MnO

+ 16 H
+
10 CO
2
+ 2Mn
2+
+ 8H
2
O
p dng quy tc ng lng, ta c:
S lg ca
4
2
2
C O

= s lg ca
4
MnO

2
2 4
4
C O MnO
S S


2
2
4 4 4
2
2
4
C O
MnO N(MnO )
C O
m
V .C

1000

2 2 4 4 4
2 2 4
H C O MnO M(MnO )
H C O
V .5.C
m .2

1000 M


26
2 2 4
4 4
2 2 4
H C O
MnO M(MnO )
H C O
V .5.C .
m
1000.2
M


2 2 4
H C O
30, 50.5.0, 01080.90
m 0, 074115( )
1000.2
g
Suy ra: ( )
2 2 4
' 4
H C O
0, 074115
n 8, 235.10 mol .
90


S mol H
2
C
2
O
4
phn ng vi MnO
2
l: ( )
2 2 4 2 2 4 2 2 4
" ' 3
H C O H C O H C O
n n n 1,8065.10 mol

Da vo phng trnh (1), ta c:
2 2 2 2 2 4 2
3
MnO MnO MnO H C O MnO
m n . M n .M 1,8065.10 .87 0,1572( ) g

Suy ra: 2
0,1572
% MnO .100% 59, 77%
0, 2630

Vy % MnO
2
trong qung pirolusit l 59,77%.
BI 10: Tnh s gam axit oxalic H
2
C
2
O
4
.2H
2
O phi cn khi ha tan vo nc ri
chun bng dung dch KMnO
4
nng c 0,1M th phi dng khong 12-15ml
KMnO
4
? [2]
Bi gii :
Phn ng chun :
5 x
2
2 4
C O

2CO
2
+ 2e
2 x
4
MnO

+ 5e + 8H
+
Mn
2+
+ 4H
2
O
5
2
2 4
C O

+ 2
4
MnO

+ 16 H
+
10 CO
2
+ 2Mn
2+
+ 8H
2
O
p dng quy tc ng lng, ta c:
S lg ca
4
2
2
C O

= s lg ca
4
MnO

2
2 4
4
C O MnO
S S


2
2
4 4 4
2
2
4
C O
MnO N(MnO )
C O
m
V .C

1000

2 2 4 2 4 4
2 2 4 2
H C O .2H O MnO M(MnO )
H C O .2H O
V .5.C
m .2

M 1000


27
2 2 4 2 2 2 4 2
4 4 4 4
2 2 4 2
H C O .2H O H C O .2H O
M(MnO ) MnO MnO M(MnO )
H C O .2H O
5.C .V .M M .V .C
m
2000 400


Trng hp 1: dng 12ml dung dch KMnO
4
:
2 2 4 2
H C O .2H O
126.12.0,1
m 0,378( )
400
g
Trng hp 2: dng 15ml dung dch KMnO
4
:
2 2 4 2
H C O .2H O
126.15.0,1
m 0, 4725( )
400
g
Vy, cn phi cn 0,378-0,4725 gam axit oxalic H
2
C
2
O
4
.2H
2
O khi ha tan vo
nc ri chun bng dung dch KMnO
4
nng c 0,1M th dng khong 12-15ml
KMnO
4
.
BI 11: C hai dung dch KMnO
4
A v B. Dung dch A c chun T
KMnO4
=
0,01507 v 20ml dung dch B tng ng vi 0,1200g Fe. Tnh t l th tch hai dung
dch A v B phi trn ln c c dung dch KMnO
4
c kh nng oxi ha nh dung
dch K
2
Cr
2
O
7
0,3330N ( mi trng axit)? [2]
Bi gii:
Ta c: 0,1200g Fe =
0,1200
56
ion g Fe
2+
=
0,1200
56
ng lng gam ca Fe
2+
=
0,1200
56

ng lng gam
4
MnO

(trong 20ml dung dch B)

Gi th tch cc dung dch A v B phi ly trn l V
A
(ml) v V
B
(ml).
i vi dung dch B:
4
Fe
MnO (B)
S S

4
B
N(MnO )
Fe Fe
Fe Fe
V .C
m m

1000 M

4
N(MnO )
Fe
Fe B
C
m 0,1200
=
1000 M .V 56.20

Ta c: s lg ca
4
MnO

trong V
A
(ml) + s lg ca
4
MnO

trong V
B
(ml) = s lg ca
K
2
Cr
2
O
7
trong (V
A
+ V
B
) (ml).
28
( )
2 2 7
4 4
K Cr O A B
MnO (A) MnO (B)
S S S

+
+
2 2 7 4 4
A B
A B N(K Cr O ) N(MnO ) N(MnO )
V .C V .C
(V V ). C

1000 1000 1000
+
+
2 2 7 4 4
4
A B
A B N(K Cr O ) M(MnO ) N(MnO )
KMnO
V .T V .C
(V V ). C
.5
M 1000 1000
+
+

( )
A B A B
0,3330. V V 0, 01507.5.V 0,1200.V

158 56.20 1000
+
+
Suy ra :
A
B
0,1200 0, 333
( - )
V
56.20 1000
1,574
0, 333 0, 01507.5
V
1000 158

Vy t l cc dung dch KMnO

4
cn phi trn l :
A
B
V
1,574
V

.
II.2. Bi tp phng php chun icromat:
II.2.1. Phn ng chun l:
6 x Fe
2+
Fe
3+
+ e

2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
6Fe
2+
+
2
2 7
Cr O

+ 14H
+
2Cr
3+
+6Fe
3+
+ 7H
2
O
Trc im tng ng
Khi trong dung dch ang d Fe
2+
nn th ti thi im ny c tnh da vo cp ca
st.Theo phng trnh Nec ta c:
E
t
= 3 2
0
Fe / Fe
E
+ + +
3
2
0, 059
log
1
Fe
Fe
+
+
1
]
1
]
2
Fe
+
1
]
=
0 0
0
6
i
i
C V CV
V V

+

3
0
6
i
i
CV
Fe
V V
+
1
]
+
E
t
= 3 2
0
Fe / Fe
E
+ + +
0 0
6 0, 059
log
1 6
i
i
CV
C V CV
0 0
6
V
i
CV
P
C V

29
Nn chia t v mu ca biu thc di log cho C
0
V
0
, ta c:
E
t
= 3 2
0
Fe / Fe
E
+ + +
0, 059log
1
P
P
Thay q = P-1 ta c : E
t
= 3 2
0
Fe / Fe
E
+ + +
1
0, 059log
q
q
+

Ti im tng ng
Th c tnh da vo hn hp ca 2 cp:
3 2
2 3
2 7
3 2 2 3
2 7
3
0
2 /
14
2
2 7
0
2
/
3
14
3 2
2 7
0 0
2
/ /
2 3
E 0, 059log
.
6E 6 0, 059log
. .
7E = 6 0, 059log
.
td
Fe Fe
td
Cr O Cr
td
Fe Fe Cr O Cr
Fe
E
Fe
Cr O H
E
Cr
Fe Cr O H
E E
Fe Cr
+ +
+
+ + +
+
+
+
+
+ +
+ +
1
]
+
1
]
1 1
] ]
+
1
]
1 1 1
] ] ]
+ +
1 1
] ]
Ti im tng ng
2 2
2 7
6 Fe Cr O
+
1 1
] ]
v
3 3
3 Fe Cr
+ +
1 1
] ]
Vic tnh th ti im tng ng ph thuc vo
3
Fe
+
1
]
hoc
3
Cr
+
1
]
Tnh theo
3
Fe
+
1
]
ta c:
3 2 2 3
2 7
14
3 2
2 7
0 0
t 2 / /
3
2
2 7
. .
7E = 6 0, 059log
6 .
3

Fe Fe Cr O Cr
Fe Cr O H
E E
Fe
Cr O
+ + +
+ +
+

1 1 1
] ] ]
+ +
_ 1
]
1
]

,
3 2 2 3
2 7
14
0 0
t
3 / /
7E = 6 0, 059log
6.
9

Fe Fe Cr O Cr
H
E E
Fe
+ + +
+
+
1
]
+ +
1
]
3 2 2 3
2 7
0 0
/ / 3
t
6
0, 059 0, 059 2
E = .14log log
7 7 7 3
Fe Fe Cr O Cr

E E
H Fe
+ + +
+ +
+
1 1 +
] ]
Hay:
30

3 2 2 3
2 7
0 0
/ / 3
t
6
0, 059 2
E = 0,118 log
7 7 3
Fe Fe Cr O Cr

E E
pH Fe
+ + +
+
+
1
]
(1)
Tuy nhin do ti im tng ng gi tr sau cng trong biu thc (1) khng ln so
vi gi tr u nn ta c biu thc cui cng l:
3 2 2 3
0 0
/ /
t
6
E = 0,118
7
Fe Fe TiO Ti

E E
pH
+ + + +
+

Nu pH = 0 th:
3 2 2 3
0 0
/ /
t
6
0, 77 6.1, 33
E = 1, 25
7 7
Fe Fe TiO Ti

E E
V
+ + + +
+
+

Sau im tng ng
Lc cho d dung dch Cr
2
O
7
2-
nn th ti thi im ny c tnh da vo cp oxh-kh
ca crm.
2 3
2 7
14
2
2 7
0
2 / 2
3
0, 059
log
6
c
Cr O Cr
Cr O H
E E
Cr
+
+
+
+
1 1
] ]
+
1
]
(3)
Vi
2 0 0 0 0
2 7
0 0 0
6
6( ) 6( )
i i
i i i
CV C V CV C V
Cr O
V V V V V V

1
]
+ + +
3 0 0
0
3( )
i
C V
Cr
V V
+
1
]
+
Thay
2
2 7
Cr O

1
]
v
3
Cr
+
1
]
vo (3)
[ ]
2 3
2 7
2 3
2 7
2
0 0 0 0
2 /
0 0 0
0 0 0 0
/
0 0 0 0
3( ) 6 14.0, 059 0, 059
log log .
6 6 6( ) ( )
6 ( ) 14.0, 059 0, 059 3
log log .
6 6 2
i i
c
Cr O Cr
i
i i
c
Cr O Cr
V V CV C V
E E H
V V C V
CV C V V V
E E H
C V C V
+
+
+
+
+
1 + +
]
+
+
1 + +
]
Trong v:
3 0 0
0
3( )
i
C V
Cr
V V
+
1
]
+

3 0 0
0
2
2
3( )
i
C V
Cr
V V
+
1
]
+
Mt khc chia c t v mu ca biu thc
0 0
0 0
6
i
CV C V
C V

cho C
0
V
0
(lu : P=
0 0
6
i
CV
C V
v chuyn q = P-1 th biu thc sau cng l:
31

2 3
2 7
0 3
/
14.0, 059 0, 059 0.059
log log log2
6 6 6
c
Cr O Cr
E E H q Cr
+
+ +
1 1 + +
] ]
(4)
Gi tr sau cng ca biu thc (4) v cng b nn:
2 3
2 7
0
/
14.0, 059 0, 059
log log
6 6
c
Cr O Cr
E E H q
+
+
1 + +
]
II.2.2. Mt s bi tp lin quan:
BI 1: Tnh sai s chun khi chun Fe
2+
0,1N bng dung dch Cr
2
O
7
2-
0,1N trong mi trng axit c pH=0 v kt thc chun th bng:
a, 1V.
b, 1,3V.
Cho 3 2 2 3
2 7
0 0
Fe /Fe Cr O /Cr
E 0, 77V; E 1,33V.
+ + +

[1]
Bi gii :
a) Ta c: pH = 0

3 2 2 3
2 7
0 0
/ /
t
6
0.77 6.1, 33
E = 1, 25
7 7
Fe Fe Cr O Cr

E E
V
+ + +
+
+

V chun Fe
2+
bng dung dch Cr
2
O
7
2-
c ng cong chun i ln m E
t
=1,25V
nn kt thc chun th bng 1V l dng thi im trc im tng ng
Ta c:
3 2
0
t
Fe / Fe
E E
+ +

+
1
0, 059log
q
q
+

1
1 0, 77 0, 059log
q
q
+
+

4
1, 264.10 0, 01264% q


32
b) Kt thc chun th bng 1,3V tc l dng thi im sau im tng ng
Ta c:
2 3
2 7
0
/
14.0, 059 0, 059
log log
6 6
c
Cr O Cr
E E H q
+
+
1 + +
]
V: pH =0 nn:
2 3
2 7
0
/
0, 059
log
6
c
Cr O Cr
E E q
+
+

0, 059
1, 3 1,33 log
6
q +

4
8, 895.10 0, 08895% q


BI 2 : Chun 100ml dung dch FeSO
4
bng dung dch K
2
Cr
2
O
7
0,02M
pH = 0. Hy tnh th in cc ca dung dch nu sai s ca chun l -0,2%. Cho
3 2 2 3
2 7
0 0
Fe /Fe Cr O /Cr
E 0, 77V; E 1, 33V.
+ + +

[1]
Bi gii:
Sai s chun l q=-0,2% tc l chun dng trc im tng ng
T lp lun trn ta c:
E
t
= 3 2
0
Fe / Fe
E
+ + +
1
0, 059log
q
q
+

(1)
0, 2
Thay: q 0, 2%
100

o (1) v
0, 2
1
100
0, 77 0, 059log 0,929
0, 2
100
t
E V

+
+
Hay: E
t
=0,929V.
33
BI 3:

Chun 100 dung dch FeSO
4
0,03M bng dung dch K
2
Cr
2
O
7
0,06N
pH=1. Tnh th in cc trong hn hp khi thm :
a, 49ml dung dch K
2
Cr
2
O
7
.
b, 50ml dung dch K
2
Cr
2
O
7.
c, 50,5ml dung dch K
2
Cr
2
O
7
. [2]
Bi gii :
Ti im tng ng:

2 2
2 7
Fe Cr O
S S
+

2 2 2 2
2 7 2 7
( ) ( ) N Fe Fe N Cr O Cr O
C V C V
+ +

0,03.100=0,06.
2
2 7
Cr O
V


2
2 7
Cr O
V

=
0, 03.100
50
0, 06

(ml)
a) Khi thm 49ml tc l dng trc im tng ng

t
t
49 50
% 100% .100 2%
50
c

V V
q
V


Trc im tng ng
E
t
= 3 2
0
Fe / Fe
E
+ + +
1
0, 059log
q
q
+

2
1
100
0, 77 0, 059log 0,87
2
100
t
E V

+
+
Hay: E
t
= 0,87V.
b ) Khi thm 50ml tc l dng im tng ng
Ti im tng ng th:
34
3 2 2 3
2 7
0 0
/ /
t
6
E = 0,118
7
Fe Fe Cr O Cr

E E
pH
+ + +
+

Vi pH = 1 ta c:
0, 77 6.1.33
0,118.1 1,132
7
t
E V
+

Hay: E
t
= 1,132V.
c) Khi thm 50,5ml tc l dng sau im tng ng:
t
t
50, 5 50
% 100% .100 2%
50
c

V V
q
V

Sau im tng ng ta c:
2 3
2 7
0
/
14.0, 059 0, 059
log log
6 6
c
Cr O Cr
E E H q
+
+
1 + +
]
V pH =1 nn:
2 3
2 7
0 1
/
14.0, 059 0, 059 2
log10 log
6 6 100
c
Cr O Cr
E E
+

+ +

14.0, 059 0, 059 2
1,33 log 1,18
6 6 100
c
E V +
Hay: E
c
=1,18V.
BI 4 : Mt mu phn tch c cha MnO
2
v tp cht tr . xc nh % MnO
2
c trong mu , ngi ta ch ha 0,25 g mu phn tch vi 25 ml H
2
C
2
O
4
0,25 N .Cho
thm 5ml dung dch HNO
3
1M kt ta hon ton , sau cho vo dung dch 1ml KI
10% v 0,5 ml h tinh bt .Chun hn hp trn bng K
2
Cr
2
O
7
0,02 M th ht 10,75
ml dung dch chuyn t mu xanh nht sang mu xanh m .
a) Hy gii thch ni dung th nghim trn bng phng trnh phn ng .
b) Tnh % MnO
2
trong mu phn tch . [2]
Bi gii :
a) Cc phn ng ln lt l:
35
MnO
2
+ 2e +4H
+
Mn
2+
+ 2H
2
O
H
2
C
2
O
4
2H
+
+ C
2
O
4
2-

C
2
O
4
2-
2CO
2
+2e
H
2
C
2
O
4
+ MnO
2
+ 2H
+
Mn
2+
+ 2CO
2
+2H
2
O

(1)
3 x H
2
C
2
O
4
2H
+
+ C
2
O
4
2-
3 x C
2
O
4
2-
2CO
2
+2e
2 x HNO
3
+ 3H
+
+ 3e NO + 2H
2
O
3H
2
C
2
O
4
+ 2HNO
3
6CO
2
+ 4H
2
O + 2NO (2)
6 x Mn
2+
+ 4H
2
O MnO
4
-
+ 8H
+
+ 5e
5 x
2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
5
2
2 7
Cr O

+ 6Mn
2+
+ 22H
+
10Cr
3+
+ 6MnO
4
-
+ 11H
2
O (3)


2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
3 x 2I
-


I
2
+ 2e

2
2 7
Cr O


+ 6I
-
+ 14H
+
2Cr
3+
+ 3I
2
+ 7H
2
O (4)
T phng trnh ta c: mu xanh nht l mu ca ion Cr
3+
, cn xanh m l do iot sinh
ra (4) kt hp vi h tinh bt nn c mu xanh m . Nn ta thy hin tng dung
dch chuyn t mu xanh nht sang mu xanh m.
b) Ta c :
2 2 4
H C O
0, 25.25
S
1000

= 6,25. 10
-3

2 2 7
K Cr O
0, 02.10, 75.6
S
1000

= 1,29.10
-3

2
8 8
MnO
6, 25.10 1, 29.10
S
2

= 2,48.10
-3
Khi lng MnO
2
trong mu phn tch l : 2,48

. 10
-3


. 87 = 0,215 (g)
Vy phn trm MnO
2
trong mu phn tch l :
36
% MnO
2
=
0, 215.100
0, 25
= 86 %
BI 5: Tnh sai s chun 100ml dung dch FeSO
4
0,100M bng dung dch
K
2
Cr
2
O
7
0,050M pH = 0 n xut hin mu tm r ca iphenylaminsunfonat
In
ox
+ 2e In
kh
(
In /In
ox kh
0
E 0,840V

0
25 C)
. [2]
Bi gii:
Th in cc ti im chuyn mu:
E =
In /In
ox kh
0
E
+
0, 059
2
= 0,87 V
t
3
t
0, 771 6.1, 33 0, 059 1
E .lg
7 7 2 Cr

+
+
+
1
]
(1)
Ta c:
3 2
t
t
0,1.100 0,1.100
V 33, 33ml; Cr 2,50.10
0, 05.6 3.133, 33

+
1
]
(2)
Thay (2) vo (1), ta c :
t 2
0, 771 6.1, 33 0, 059 1
E .lg
7 7 2.2,50.10

+
+
= 1,261(V).
Bi v: E = 0,87 V < E
t
(trc im tng ng), nn:
q 1
E 0,87 0, 771 0, 059.lg
q
+
+

Suy ra:
q 1
lg
q
+

=
0,87 0, 771
0, 059

= 1,68
q 1
q
+

= 47,9 q = -0,020 = -2%.

BI 6: Ha tan 1g qung crom trong axit, oxi ha Cr
3+
thnh
2
2 7
Cr O

. Sau khi
phn hy lng d cht oxi ha, ngi ta pha long dung dch thnh 100ml. Ly
20ml dung dch ny cho vo 25ml dung dch FeSO
4
trong H
2
SO
4
2N. Chun lng
d FeSO
4
ht 7,50ml dung dch K
2
Cr
2
O
7
0,01500M. Bit rng 25ml FeSO
4
tng
ng vi 35ml K
2
Cr
2
O
7
. Tnh thnh phn % ca Cr trong qung? [2]
37
Bi gii:
Ta c qu trnh ch ha: 2Cr 2Cr
3+

2
2 7
Cr O

Suy ra : 2 . s lg ca Cr = s lg ca
2
2 7
Cr O

2
2 7
Cr
Cr O
2S S


(1)
Cc phng trnh xy ra trong hn hp khi cho dung dch FeSO
4
vo :
6 x Fe
2+
Fe
3+
+ e

2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
6Fe
2+
+
2
2 7
Cr O

+ 14H
+
2Cr
3+
+ 6Fe
3+
+ 7H
2
O
p dng quy tc ng lng :
S lg ca
2
2 7
Cr O

= s lg ca Fe
2+
2 2
2 7
Cr O Fe
S = S
+

(2)
T ( 1) v (2), ta c : 2
Cr
Fe
2S = S
+
Theo gi thit: 25ml FeSO
4
tng ng vi 35ml K
2
Cr
2
O
7
.
2 2
2 7
Cr O Fe
S = S
+

2 2 2 2 2 2 2 2
2 7 2 7 2 7 2 7
Cr O N(Cr O ) Fe N(Fe ) Cr O M(Cr O ) Fe M(Fe )
V .C V .C 6.V .C V .C
+ + + +

2 2
2 7 2 7
2
2
Cr O M(Cr O )
M(Fe )
Fe
6.V .C
6.35.0, 01500
C 0,126
V 25
M

+
+

Chun FeSO
4
d ht 7,50ml K
2
Cr
2
O
7
, nn:
S lg ca Fe
2+
(d) = s lg ca
2
2 7
Cr O

S lg ca Fe
2+
ban u - S lg ca Fe
2+
phn ng = s lg ca
2
2 7
Cr O

S lg ca Fe
2+
ban u 2. S lg ca Cr = s lg ca
2
2 7
Cr O

2 2
2 7
Cr
Fe Cr O
S 2.S S
+

( )
2 2
2 2
2 7 2 7
Fe N Fe
Cr O N(Cr O )
Cr
Cr
V .C
V .C
m 20
2. .
1000 100 1000
+ +

38
( )
2 2
2 2
2 7 2 7
Fe M Fe
Cr O M(Cr O )
Cr
Cr
V .C
6.V .C
m 20
2. .
1000 100 1000 M
+ +


Cr
25.0,126 m .20 6.7,50.0, 01500
2.
1000 52.100 1000

m
Cr
= 0,32175(g).
Vy, % Cr trong qung l :
0, 32175
%Cr .100% 32,18%
1

.
BI 7 : un chy 0,935g qung cromit vi Na
2
O
2
oxi ha Cr thnh
2
4
CrO
. Cho
khi chy vo nc, un si n phn hy ht Na
2
O
2
. Axit ha dung dch, thm
50,00ml FeSO
4
0,080N. Chun lng Fe
2+
d ht 14,85ml K
2
Cr
2
O
7
0,0200N. Tnh
thnh phn % ca crom trong qung ? [2]
Bi gii :
Qu trnh ch ha : Cr
2
4
CrO

Suy ra :
2
4
Cr
CrO
S S

(1)
3 x Fe
2+
Fe
3+
+ e

2
4
CrO

+ 8H
+
+ 3e Cr
3+
+ 4H
2
O
3Fe
2+
+
2
4
CrO

+ 8H
+
Cr
3+
+ 3Fe
3+
+ 4H
2
O
Ta c: s lg ca
2
4
CrO

= s lg ca Fe
2+
phn ng

2+ 2
4
Fe CrO
S S

(2)
T (1) v (2), suy ra : 2
Cr
S S
Fe
+

Mt khc : lng FeSO

4
d c chun ht bi 14,85ml dung dch K
2
Cr
2
O
7
0,0200N
nn :
s lg ca Fe
2+
d = s lg ca K
2
Cr
2
O
7
.
s lg ca Fe
2+
ban u - s lg ca Fe
2+
phn ng = s lg ca K
2
Cr
2
O
7
.
s lg ca Fe
2+
ban u - s lg ca Cr = s lg ca K
2
Cr
2
O
7
.
2 2
2 2 7 2 2 7
K Cr O N(K Cr O ) Fe N(Fe )
Cr
Cr
V .C
V .C
m

1000 1000
+ +

39
2 2
2 2 7 2 2 7
K Cr O N(K Cr O ) Fe N(Fe )
Cr
Cr
V .C
V .C
m

1000 1000 M
+ +

Cr
50, 00.0, 080 m 14,85.0, 0200

1000 52 1000

m
Cr
= 0,193 (g).
Vy, %Cr trong qung l :
0,193
%Cr .100% 20.64%
0, 935

II.3. Bi tp chun bng iot:
BI 1 : Cho 1g mu lum ( thnh phn H
2
SO
4 ,
SO
3
v SO
2
) vo nc pha
thnh 250 ml . Chn 25 ml dung dch ht 21,2 ml NaOH 0,1 M ( chun n pH
= 4) . Mc khc , cng chun 100 ml dung dch phn tch trn bng dung dch It
ht 37 ml dung dch I
2
0,025 N . Tnh thnh phn % cc cu t c trong mu? ( Bit
H
2
SO
3
c pK
1
=1,76 ; pK
2
= 7,21 ). [1]
Bi gii:
lum ( H
2
SO
4
; SO
3
; SO
2
) vo nc pha thnh 250 ml ta c dung dch c cha
H
2
SO
4
; H
2
SO
3
do:
SO
3
+H
2
O H
2
SO
4
SO
2
+H
2
O H
2
SO
3
Ta c :
H
2
SO
3
H
+
+ HSO
3
-
K
1
= 10
-1,76

HSO
3
-
H
+
+SO
3
2-
K
2
= 10
-7,21
Nhn xt :
pH =
1, 76 7, 21
2
+
= 4,49 pH =4
Chun n pH = 4:
H
2
SO
4
+ 2NaOH Na
2
SO
4
+ 2H
2
O
H
2
SO
3
+ NaOH NaHSO
3
+ H
2
O
40
Ta li c:
2 4
H SO
H2SO4
M
98
49
2 2

3
3
SO
SO
M
80
40
2 2

2
2
SO
SO
M
64
1

Gi x l s gam H
2
SO
4
, y l s gam SO
3
, z l s gam SO
2
.

Ta c: S lg H
2
SO
4
+ S lg SO
3
+ S lg SO
2
= S lg NaOH
25 x y z 0,1.21, 2
.
250 49 40 64 1000
_
+ +

,
x y z
0, 0212
49 40 64
_
+ +

,
(1)
Chun vi I
2
:
SO
2
+ 2 H
2
+ I
2
H
2
SO
4
+ 2HI
Ta c:
2
2
SO
SO
M
64
32
2 2

p dng quy tc ng lng:
S lg SO
2
= S lg I
2

z.100 0, 025.2.37

32.250 1000

z = 0,148 (2)
Mt khc: x +y +z = 1 (3)
Gii phng trnh (1) ,(2) ,(3) ta c:
x = 0,5254 ; y = 0,3266 ; z = 0,1480
Vy:
Phn trm ca H
2
SO
4
trong lum l : % H
2
SO
4
=
0,525.100%
52, 54%
1

Phn trm ca SO
3
trong lum l : % SO
3
=
0,3266.100%
32, 66%
1

Phn trm ca SO
2
trong lum l : % SO
2
= 100-52,54 -32,66 = 14,8 %
41
BI 2: Ha tan 0,2940g K
2
Cr
2
O
7
trong bnh nh mc 200ml ri thm nc n
vch. Axit ha 25,00ml dung dch ny bng H
2
SO
4
2N, thm KI d, chun iot sinh
ra ht 10,00ml Na
2
S
2
O
3
. Tnh nng mol/l v chun ca dung dch Na
2
S
2
O
3
? [2]
Bi gii :
3 x 2I
-
I
2
+ 2e

2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O

2
2 7
Cr O

+ 14H
+
+ 6I
-
2Cr
3+
+ 3I
2
+ 7H
2
O
p dng nh lut ng lng:
2
2
2 7
I
Cr O
S S

(1)
Lng I
2
gii phng ra c chun bng Na
2
S
2
O
3
, phng trnh chun :
2
2 2 3
I 2 S O

+

2
4 6
2I S O

+
Ta li c:
2
2
2 3
I
S O
S S

(2)
T (1) v (2), suy ra:
2
2 7
Cr O
S

=
2
2 3
S O
S

2 2 2
2 3 2 3 2 7
2
2 7
S O N(S O ) Cr O
Cr O
V .C m
25
.
1000 100

2 2 2
2 3 2 3 2 7
2
2 7
S O M(S O ) Cr O
Cr O
2.V .C 6.m
25
.
1000 200 M

2 2
2 7 2 7
2
2 3
2 2 2 2
2 7 2 3 2 7 2 3
Cr O Cr O
M(S O )
Cr O S O Cr O S O
6.m .1000 375.m
25
C .
.2.V . 200 .V M M

2
2 3
M(S O )
375.0, 2940
C 0, 0375( )
294.10, 00
M

chun ca dung dch Na
2
S
2
O
3
l:

2 2 3 2 2 3
2 2 3
M(Na S O ) Na S O 3
Na S O
C .M
0, 0375.158
T 5,925.10
1000 1000


BI 3: Lm kt ta ht ion Pb
2+
trong mt dung dch mui ch di dng PbCrO
4
.
Ha tan kt ta PbCrO
4
thu c trong HCl khi c KI d. Chun iot gii phng ra
ht 31,5ml Na
2
S
2
O
3
0,1010M. Tnh s gam ch trong dung dch? [2]
42
Bi gii:
Qu trn lm kt ta ch:
Pb
2+
+
2
4
CrO

PbCrO
4
Ta c:
2 2
4
4
PbCrO
Pb CrO
S S S
+

(1)
Ha tan kt ta trong HCl c KI:
2 x
2
4
CrO

+ 8H
+
+ 3e Cr
3+
+ 4H
2
O
3 x 2I
-
I
2
+ 2e
2
2
4
CrO

+ 16H
+
+ 6I
-
2Cr
3+
+ 3I
2
+ 8H
2
O
Ta c: s lg ca
2
4
CrO

= s lg ca I
2

2
2
4
I
CrO
S S

(2)
Chun I
2
sinh ra bng Na
2
S
2
O
3
, phng trnh chun :
2
2 2 3
I 2 S O

+

2
4 6
2I S O

+
Nn:
2
2
2 3
I
S O
S S

(3)
T (1), (2) v (3), ta c : 2
Pb
S
+ =
2
2 3
S O
S

2 2
2
2 3 2 3
2
S O N(S O )
Pb
Pb
V .C
m

1000

+
+

2 2
2
2 3 2 3
2
S O M(S O )
Pb
Pb
V .2.C
m

1000 M

+
+

2 2 2
2 3 2 3
2
S O M(S O ) Pb
Pb
V .2.C .
31,5.0,1010.2.207
m 1, 317( )
1000 1000
M
g
+
+

BI 4 : Ha tan 0,700g mt hp kim ng trong axit ri pha long vi nc thnh
200ml. Axit ha 30ml dung dch ny bng H
2
SO
4
v KI d. Chun iot gii phng ra
ht 7,00ml Na
2
S
2
O
3
0,1000M. Tnh thnh phn % ca Cu trong hp kim? [2]
Bi gii :
Qu trnh axit ha: Cu Cu
2+
+ 2e
Trong mi trng H
+
v c KI d:
2 x Cu
2+
+ 1e Cu
+
43
2I
-
I
2
+ 2e
2 x Cu
+
+ I
-
CuI
2Cu
2+
+ 4I
-
I
2
+ 2CuI (1)
Lng iot gii phng ra c chun bng Na
2
S
2
O
3
:
2
2 2 3
I 2 S O

+
2I

+
2
4 6
S O

(2 )
p dng nh lut ng lng cho phng trnh (1) v (2), ta c :
2
2
Cu I
Cu
S S S
+


V :
2
2
2 3
I
S O
S S

Suy ra:
Cu
S
=
2
2 3
S O
S

2 2
2 3 2 3
S O N(S O )
Cu
Cu
V .C
m 30
.
200 1000

2 2
2 3 2 3
S O M(S O )
Cu
Cu
V .2.C
m 30
.
200 1000 M


2 2
2 3 2 3
Cu
S O M(S O )
Cu
V .2.C . .200
m
1000.30
M


Cu
7, 00.2.0,1000.64.200
m 0, 597( )
1000.30
g
Vy, % Cu trong hp kim ng l:
0,597
% Cu .100% 85,33%
0, 700

.
BI 5: Ha tan 0,600 g mt mu phn tch cha Pb
2
O
3
v Pb
3
O
4
trong axit ri lm
kt ta ht ch di dng PbCrO
4
. Ha tan kt ta trong axit khi c KI d. Chun
iot gii phng ra ht 35,04ml Na
2
S
2
O
3
0,200M. Mt khc, khi cho tc dng HCl c
vi 0,600 g mu phn tch, lng clo thot ra c hp th hon ton trong 50,00ml
KI 10%. chun iot gii phng ra phi dng 9,36ml Na
2
S
2
O
3
0,200M. Tnh hm
lng % ca cc cht c trong mu? [2]
Bi gii:
Qu trnh axit ha hn hp xy ra nh sau:
44
Pb
2
O
3
2Pb
2+
2PbCrO
4

2
2 7
Cr O

(1)
Pb
3
O
4
3Pb
2+
3PbCrO
4

3
2
2
2 7
Cr O

(2)
2
2 7
Cr O

+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
2I
-
I
2
+ 2e
2
2 2 3
I 2 S O

+

2
4 6
2I S O

+
Gi x l s gam ca Pb
2
O
3
v y l s gam ca Pb
3
O
4
.
Theo phng trnh (1) v (2), ta c:
S mol Pb
2+
= s mol
2
4
CrO

= 2. s mol
2
2 7
Cr O

= 2. s lg
2
2 7
Cr O

.
1
6
= s lg Na
2
S
2
O
3
.
1
3
Suy ra:
2 3 3 4
3
Pb O Pb O
2x 3y 0, 200.35, 04
2, 336.10
M M 1000.3

+
3
2x 3y
2, 336.10
462 685

+
(1)
Cho mu tc dng vi HCl c th PbO
2
b kh:
Pb
2
O
3
PbO + PbO
2
Pb
3
O
4
2PbO + PbO
2
PbO + 2HCl PbCl
2
+ H
2
O
PbO
2
+ 4H
+
+ 2Cl
-
+ 2e PbCl
2
+ 2H
2
O
2Cl
-
Cl
2
+ 2e
p dng quy tc ng lng:
S lg PbO
2
= s lg Cl
2
= s lg I
2
= s lg Na
2
S
2
O
3
2 3 3 4
3
Pb O Pb O
2x 2y 0, 200.9, 36
1,872.10
M M 1000

+

3
2x 2y
1,872.10
462 685

+
(2)
Gii (1) v (2), ta c:
45
( )
( )
2 3
3 4
Pb O
Pb O
x m 0, 21801 g
y m 0, 31784 g .


Vy :

2 3
% Pb O 36, 34 %
3 4
%Pb O 53 %
46
C. KT LUN
Qua vic tm hiu, nghin cu v phn dng bi tp ti thy ha hc phn tch
ng mt vai tr quan trng trong vic gip hc sinh hnh thnh k nng v k xo gii
mt s bi tp lin quan.
Tuy nhin, trong qu trnh thc hin ti ny ti cng gp mt s kh khn trong
vic gii mt s bi tp kh, v th ti da vo mt s ti liu lin quan gii
nhng bi tp ny.
i vi tiu lun ny, ti ch nghin cu v mng phng php chun oxi ha
kh trong ha hc phn tch nh lng. Nu c thi gian v iu kin ti xin ha s
nghin cu su hn tip tc b sung v chnh l ti liu ti c hon thin
hn.
47
D. TI LIU THAM KHO
1. Nguyn Hu Hin (2010), Phn Tch nh Lng, i hc s phm Hu.
2. Nguyn Tinh Dung (1982), Bi tp Ha Hc Phn Tch, Nh xut bn Gio dc.
3. Nguyn Tinh Dung, Ha Hc Phn Tch, Nh xut bn Gio dc.
4. http://www.ngocbinh.dayhoahoc.com.
5. http://www.tailieuvn.com.
48