MT S TNH CHT V NG DNG CA CROM

TS Vi Anh Tun Khoa Ha hc

Trng i hc KHTN i hc Quc gia H Ni
Crom l nguyn t kim loi chuyn tip thuc nhm VIB ca bng h thng tun hon. Crom c cu
hnh electron lp v ha tr l 3d54s1. S oxi ha c trng ca crom l +3 v +6. Tn gi ca crom xut
pht t ting Hy Lp "chroma" c ngha l mu sc v cc hp cht ca crom u c mu.
Crom l kim loi mu trng bc. Do c s electron c thn ti a nn bn ca lin kt trong tinh th
crom l ln nht, v vy crom c nhit si, nhit nng chy v cng rt cao (t onc = 1907oC; tos =
2671oC, cng theo thang Mohs: 8,5).
1. iu ch crom

Khong vt chnh ca crom l st cromit (FeCr2O4). Nhng nc giu m qung crom l Nam Phi,
Kazakhstan, n , Nga, Th Nh K v Zimbabwe. Nc ta c mt m sa khong cromit kh ln C
nh, Thanh Ha.
Trong cng nghip lng ln crom c sn xut t qung di dng hp kim ferocrom cha 50 70%
crom, c sn xut bng cch dng than cc kh qung cromit trong l in:
to

Fe(CrO2)2 + 4 C

Fe + 2 Cr + 4 CO

iu ch crom tinh khit ngi ta phi tch st ra khi qung cromit theo quy trnh sau: Qung
cromit c un nng chy vi hn hp canxi cacbonat v natri cacbonat v c mt khng kh. Crom b oxi
ha thnh cromat v st chuyn thnh Fe2O3. Ha tan hn hp vo nc, tch phn oxit st khng tan thu
c dung dch cromat. Thm axit sunfuric chuyn cromat thnh dicromat:
to

4 FeCr2O4 + 8 Na2CO3 + 7 O2

8 Na2CrO4 + 2 Fe2O3 + 8 CO2

2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O

Kh dicromat thnh crom (III) oxit bng cacbon. Tip theo kh crom (III) oxit bng nhm s thu c
crom kim loi:
to

Na2Cr2O7 + 2 C
Cr2O3 + 2 Al

Cr2O3 + Na2CO3 + CO
2 Cr + Al2O3

Cu 1.1. (a) Vit cc phng trnh ho hc t Na2Cr2O7, C (than ), Al (bt nhm) v cc iu kin
cn thit thu c Cr.
(b) CrO2Cl2 (cromyl clorua) l mt ho cht quan trng. Hy vit cc phng trnh ho hc to ra
CrO2Cl2 t:
i. CrO3 tc dng vi axit HCl.
ii. Cho K2Cr2O7 tc dng vi KCl trong H2SO4 c, nng.
(c) Thm cht thch hp v hon thnh cc phng trnh ho hc sau:
i. KNO2
ii. NaNO2

+ KNO3

+ ?

K2CrO4 + NO

+ ? + NaI I2 + NaHSO4 + NO + H2O

iii. HNO3 + P2O5 ? + N2O5

Trang 1

(a. Na2Cr2O7 + 2 C
Cr2O3 + 2 Al

to

Na2CO3 + Cr2O3 + CO

to

2 Cr + Al2O3

b. i. CrO3 + 2 HCl CrO2Cl2 + H2O

ii. K2Cr2O7 + 4 KCl + 3 H2SO4 3 K2SO4 + 2 CrO2Cl2 + 3 H2O
c. i. 3 KNO2 + KNO3 + Cr2O3 2 K2CrO4 + 4 NO
ii. 2 NaNO2 + 4 H2SO4 + 2 NaI I2 + 4 NaHSO4 + 2 NO + 2 H2O
iii. 2 HNO3 + P2O5 2 HPO3 + N2O5)
Cu 1.2. (a) Ti sao crom c kh nng th hin nhiu trng thi oxi ho? Cho bit nhng s oxi ho ph
bin ca crom?
(b) Nu v gii thch s bin i tnh cht axit baz trong dy oxit: CrO, Cr2O3, CrO3. Vit phng
trnh ho hc ca cc phn ng minh ho.
(c) Vit phng trnh ion ca cc phn ng iu ch Al2O3 v Cr2O3 t dung dch gm kali cromit v
kali aluminat.
(a. Cu hnh electron ca crom l [Cr]3d54s1, do nguyn t crom c 6 electron ha tr nn crom th
hin nhiu trng thi oxi ha; S oxi ha ph bin ca crom l +2, +3, +6.
b. i t CrO Cr2O3 CrO3 th tnh axit tng dn, tnh baz gim dn.
Gii thch: khi i t CrO Cr2O3 CrO3 th s oxi ha ca nguyn t crom tng do tnh cng ha
tr ca lin kt Cr O tng, lm cho tnh baz gim, tnh axit tng.
Trong thc t CrO l oxit axit, Cr2O3 l oxit lng tnh v CrO3 l oxit axit.
CrO + 2 H+ Cr2+ + H2O
Cr2O3 + 6 H+ 2 Cr3+ + 3 H2O
Cr2O3 + 2 OH (nng chy) 2 CrO2 + H2O
CrO3 + 2 OH CrO42 + H2O
c. Cch 1: Thm H2O2 v NaOH d vo dung dch:
2 Cr(OH)4 + 3 H2O2 + 2 OH 2 CrO42 + 8 H2O
Thm tip CO2 n d vo dung dch thu c:
Al(OH)4 + CO2 Al(OH)3 + HCO3
Lc ly kt ta em nung thu c Al2O3 tinh khit:
2 Al(OH)3 Al2O3 + 3 H2O
Thm H2SO4 n d vo phn dung dch lc, c cn dung dch kt tinh K2Cr2O7.
2 CrO4 + 2 H+ Cr2O72 + H2O
Nung K2Cr2O7 vi C thu c Cr2O3
K2Cr2O7 + 2 C K2CO3 + Cr2O3 + CO
Cch 2: Thm H2O2 v KOH d vo dung dch:
2 Cr(OH)4 + 3 H2O2 + 2 OH 2 CrO42 + 8 H2O
Thm tip CO2 n d vo dung dch thu c:
Al(OH)4 + CO2 Al(OH)3 + HCO3
Trang 2

Lc ly kt ta em nung thu c Al2O3 tinh khit:

2 Al(OH)3 Al2O3 + 3 H2O
Thm H2O2 v H2SO4 n d vo phn dung dch lc:
Cr2O72 + 8 H+ + 3 H2O2 2 Cr3+ + 3 O2 + 7 H2O
Thm NH3 long kt ta Cr3+:
Cr3+ + 3 NH3 + 3 H2O Cr(OH)3 + 3 NH4+
Lc ly kt ta em nung thu c Cr2O3 tinh khit:
2 Cr(OH)3 Cr2O3 + 3 H2O)
Cu 1.3. Ha tan hon ton 0,1331 gam mt mnh hp kim cha st v crom bng dung dch axit sunfuric
long, d to thnh cc ion Fe2+ v Cr3+. Chun dung dch thu c bng dung dch pemanganat nhit
phng thy va ht 20,08 ml dung dch. Bit rng iu kin th nghim Cr3+ khng tham gia phn ng.
Trong mt th nghim khc, ngi ta chun 10 ml dung dch axit oxalic 0,0500 M trong mi trng
axit sunfuric bng dung dch pemanganat trn thy va ht 9,75 ml dung dch.
(a) Hy vit cc phn ng xy ra dng ion rt gn.
(b) Hy tnh thnh phn % theo khi lng ca st v crom trong hp kim ban u. (Cr = 52,00; Fe =
55,85).
Mt bnh in phn cha 100 lit dung dch CrO3 nng 230 g/lit. Tin hnh in phn dung dch trong
khong thi gian 10 gi vi cng dng in 1500 A. Sau khi kt thc th nghim thy khi lng ca
catot tng ln 670 gam, bit rng c kh thot ra c catot v anot.
(c) Hy cho bit kh thot ra anot v catot?
(d) Hy tnh hiu sut ca qu trnh in phn iu ch crom.
(e) Hy tnh th tch kh thot ra catot v anot 25C v 1,00 atm.
Fe + 2 H+ Fe2+ + H2

(a.

Cr + 3 H+ Cr3+ + 3/2H2
5 Fe2+ + MnO4 + 8 H+ 5 Fe3+ + Mn2+ + 4 H2O
5 H2C2O4 + 2 MnO4 + 6 H+ 10 CO2 + 2 Mn2+ + 8 H2O
MnO4 : 0,02051 M;

b.

Fe: 86,4%; Cr: 13,6%;

CrO3 + H2O 2 H+ + CrO42

c.

CrO42 + 8 H+ + 6 e Cr + 4 H2O
Anot (+): 2 H2O O2 + 4 H+ + 4e
Catot (): 2 H+ + 2e H2
d. C:

ne

It 1500 10 3600

559,7 mol
F
96485

S mol electron do cromat nhn l:

ne'

670
6 77,3 mol
52,00

Trang 3

Hiu sut ca qu trnh in phn iu ch crom:

e. C:

ne'
77,3

100 13,8%
ne 559,7

nH 2

ne ne' 559,7 77,3

241,2 mol
2
2

nO2

ne 559,7

139,9 mol
4
4
VH 2

=>

VO2

241,2 0,082 298

5,89.103 lit
1

139,9 0,082 298

3,42.103 lit )
1

Cu 1.4. Ngun nguyn liu chnh iu ch crom l qung cromit (FeCr2O4), trong cromit st c ha
tr II.
(a) Hy xc nh s oxi ha ca crom trong cc cu t sau: Cr2O3, CrO42, Cr2O72, FeCr2O4.
(b) Hy vit phng trnh phn ng kh qung cromit bng cacbon, bit sn phm thu c l st, crom
v cacbon dioxit.
Quy trnh iu ch mui crom (III) t qung cromit nh sau: u tin oxi ha cromit bng khng kh
trong natri hidroxit nng chy to thnh natri cromat (Na2CrO4); Ha tan sn phm vo nc, axit ha dung
dch bng dung dch H2SO4 thu c dung dch c mu da cam; C cn dung dch, ly cht rn em kh
bng cacbon thu c Cr2O3; Ha tan oxit ny bng dung dch axit sunfuric thu c dung dch mui crom
(III).
(c) Hy vit cc phng trnh phn ng xy ra trong quy trnh trn.
xc nh hm lng crom trong mu qung cromit, ngi ta s dng phng php chun iot
thiosunfat. Oxi ha 5,00 g mu qung cromit bng oxi trong dung dch natri hidroxit, chuyn ton b dung
dch thu c (cha natri cromat) vo bnh nh mc 1,00 lit v nh mc n vch bng nc ct (dung
dch A). Ly 25,00 ml dung dch A cho vo bnh nn c cha dung dch m. Thm khong 3 gam KI. y
kn ming bnh v trong ti cho phn ng xy ra hon ton, sn phm to thnh l I3 v Cr3+. Chun
lng I3 sinh ra bng dung dch Na2S2O3 0,1000 M, sn phm to thnh l I v ion tetrathionat
(S4O62), thy va ht 23,10 ml dung dch.
(d) Hy vit cc phng trnh phn ng xy ra trong quy trnh phn tch trn.
(e) Hy tnh nng ca natri cromat trong dung dch A.
(g) Hy tnh thnh phn % theo khi lng ca cromit trong mu qung.
(h) Hy tnh thnh phn % theo khi lng ca crom trong mu qung.
(a. +3, +6, +6, +3;
b. FeCr2O4 + 2 C Fe + 2 Cr + 2 CO2
c. 4 FeCr2O4 + 7 O2 + 16 NaOH 2 Fe2O3 + 8 Na2CrO4 + 8 H2O
2 Na2CrO4 + 2 H2SO4 2 NaHSO4 + Na2Cr2O7 + H2O
Na2Cr2O7 + 2 C

to

Na2CO3 + Cr2O3 + CO

Cr2O3 + 3 H2SO4 Cr2(SO4)3 + 3 H2O

Trang 4

d. 4 FeCr2O4 + 7 O2 + 16 NaOH 2 Fe2O3 + 8 Na2CrO4 + 8 H2O

2 CrO42 + 9 I + 16 H+ 2 Cr3+ + 3 I3 + 8 H2O
I3 + 2 S2O32 3 I + S4O62

e. CCrO2
4

1 2
23,10 0,1000
2 3 0,0308M

25,00

g. nFeCr O 0,0308 1,0

2

=> % FeCr2O4

4
0,0154 mol
8

0,0154 223,85
100 68,94%
5,00

h. nCr 2nFeCr O 0,0308 mol

2

=> %Cr

0,0308 52,00
100 32,04% )
5,00

2. Phc cht ca crom

2.1. Phc cht crom (0)

a) Phc hexacacbonyl crom(0), Cr(CO)6
z*
x* y*
2p
2p

z
x y
s*
2s
C

s
CO

2s
O

Gin MO ca phn t CO.

Trong phn t CO, cp electron trn MO z c nng lng cao hn nhng cp electron trn MO x v
y nn c kh nng to lin kt cho nhn vi cc obitan lai ha d2sp3 trng ca nguyn t crom.

Trang 5

d2sp3
3d

4p

4s

Cr(0):

lin kt
Cr
CO

CO

CO

CO

CO

CO

lin kt Cr

CO

CO

Ngoi lin kt cho nhn (CrCO), trong hexacacbonyl cn c lin kt

cho CrCO to nn bi nhng cp electron d ca nguyn t crom vi nhng MO * trng ca phn t
CO v nh lin kt ny, cc phn t cacbonyl kim loi c lm bn thm.

Cr

-cho

Vy phc Cr(CO)6 c cu hnh bt din u v nghch t.

CO
OC

Cr

OC

CO
CO

CO
Nh vy phc Cr(CO)6 tun theo quy tc 18 electron: "Nguyn t kim loi trong cacbonyl kim loi c
khuynh hng nhn thm mt s electron ca phn t CO t c 18 electron v ha tr". Di y l
mt s phc cacbonyl kim loi tun theo quy tc 18 electron.
Cacbonyl

S electron
ha tr ca M

S electron CO
ng gp

Tng

Hnh hc phn t

Ti(CO)7

14

18

V2(CO)12

12+1

18

Cr(CO)6

12

18

Bt din u

Mn2(CO)10

10+1

18

2 bt din chung 1
nh

Fe(CO)5

10

18

Lng thp tam gic

Co2(CO)8

8+1

18

Ni(CO)4

10

18

T din

Trang 6

CO

CO
CO
OC

Mn

Mn

OC

CO
CO

OC
CO

CO

d2sp3
3d

4p

4s

Mn (0):

Mn

CO

CO

CO

CO

CO CO

Mn-Mn
Mn

CO

b) Phc crom dibenzen Cr(C6H6)2

Phn t crom dibenzen c hnh bnh kp (thuc loi hp cht c kim).
*
Cr

Gin nng l-ng cc MO ca benzen

d2sp3
3d

4p

4s

Cr (0):

Cr

MO *
Cr

MO

Trong hp cht ny, quy tc 18 electron cng c tun theo.

Cu 2.1. Cui th k 18 Ludwig Mond pht hin ra rng niken dng bt mn phn ng vi cacbon
monoxit to thnh tetracacbonyl niken, Ni(CO)4, mt cht lng khng mu, d bay hi. Phc Ni(CO)4 tun
theo quy tc 18 electron.
(a) S dng quy tc 18 electron, hy d on cng thc phc cacbonyl ca Fe(0) v Cr(0).
(b) S dng quy tc 18 electron hy d on cng thc phc nitrozyl ca Cr(0)?
(c) Hy gii thch ti sao Mn(0) v Co(0) khng th to ra cc phc cacbonyl n nhn kiu M(CO) x (M
l kim loi), m ch c th to cc phc cacbonyl c lin kt kim loi kim loi?
(d) Hy cho bit cu trc khng gian ca Ni(CO)4, Mn2(CO)10 v Co2(CO)8.
(e) Hy cho bit phc V(CO)6 v cc phc cho phn (a) v (d) l thun t hay nghch t?
Trang 7

(g) Hy gii thch ti sao cacbon monoxit lin kt vi kim loi bn hn rt nhiu so vi khi lin kt vi
bo trong hp cht kiu R3BCO; R l gc ankyl?
(h) Quy tc 18 electron cng nghim ng i vi phc ca crom v benzen.
i/ Hy vit cng thc ca phc.
ii/ Hy cho bit cng thc ca phc c cu trc tng t c iu ch bng phn ng gia bt st
vi xiclopentadien? Hy vit phng trnh phn ng iu ch phc.
(a. Fe(CO)5 v Cr(CO)6;
b. Cr(NO)4
c. Do nguyn t Mn v Co c s l electron.
d.

Ni
OC

CO

CO

CO

CO
CO
CO

OC

Mn

OC

CO
Mn
CO

OC
OC

OC
CO

CO

CO

CO
Co

Co
OC

OC

CO
CO

e. Fe(CO)5, Cr(CO)6, Ni(CO)4, Mn2(CO)10, Co2(CO)10: nghch t;

V(CO)6 thun t;
g. Do trong R3B CO khng c lin kt cho.

Cr

-cho

h. i/

Cr

ii/ Fe + 2 C5H6 Fe(C5H5)2 + H2

Fe

)
2.2. Phc cht crom (II)
Cr(II) axetat l kt ta mu v l hp cht bn nht ca Cr(II), c cu to ime
[Cr(CH3COO)2.H2O]2. Trong phn t dime lin kt Cr Cr l lin kt bn (1, 2, 1).

Trang 8

d2sp3
3d

4p

4s

Cr (II):
Cr-Cr

Cr-Cr Cr-Cr
Cr

O
H2O

Cr

O O
Cr

OH2

Cr(II) axetat c iu ch theo phn ng:

2 CrCl2 + 4 NaCH3COO + 2 H2O [Cr(CH3COO)2.H2O]2 + 4 NaCl
Cu 2.2. X l mt hp cht ca crom. Phn tch thnh phn nguyn t cho thy: Cr 27,7%; C: 25,5%; H
4,25% theo khi lng, phn cn li l oxi.
(a) Hy cho bit cng thc n gin nht ca X.
(b) Bit rng trong cng thc n gin nht c cha mt phn t nc, hy cho bit phi t cn li l
g? Hy cho bit s oxi ha ca Cr trong X.
(c) Nghin cu t tnh cho thy X c tnh nghch t, hy gii thch tnh cht ny ca hp cht X v v
cu trc khng gian ca X.
(a. Cr : C : H : O

27,7 25,5 4,25 42,55

:
:
:
0,533 : 2,125 : 4,25 : 2,66 1 : 4 : 8 : 5
52 12
1
16

=> Cng thc kinh nghim ca X l: CrC4H8O5.

b. Cr(H2O)(CH3COO)2, phi t cn li l axetat, s oxi ha ca crom: +2.
c. X l ime: [Cr(H2O)(CH3COO)2] 2.
O
H2O
O

Cr
O

O O
Cr

OH2

O
d2sp3

3d

4p

4s

Cr (II):

Cr-Cr

Cr-Cr Cr-Cr
Cr

Cu 2.3. Kim loi A c mu trng bc v c nh kim. Trong cng nghip, ngi ta dng kim loi A
m ln cc vt bng kim loi bo v cho kim loi khng b g, lp m thng ch dy khong 0,005
Trang 9

mm. Hidroxit ca A l cht B c dng A(OH)2, B l cht kt ta mu vng nhng thng ln tp cht nn c
mu hung. Khi tip xc vi khng kh, B chuyn thnh C l cht nhy c mu lc nht, khng tan trong
nc nhng tan c trong c dung dch kim cng nh dung dch axit. Cht B tan trong dung dch HCl d
cho dung dch D c mu xanh lam nhng khi c cn dung dch th li c mui rn khan mu trng, ht m
mnh. Cho dung dch D tc dng vi dung dch NaCH3COO c thu c kt ta t tan mu E. E dng
dime l hp cht c cu to c bit v l mt trong nhng cht d iu ch v bn nht ca A(II).
(a) Tm cc cht t A n E v vit cc phng trnh phn ng xy ra.
(b) Nu bn cht lin kt ca A trong dime E.
(a. A: Cr;
4 Cr(OH)2 + O2 + 2 H2O 4 Cr(OH)3
B

Cr(OH)3 + 3 H+ Cr3+ + 3 H2O

Cr(OH)3 + OH [Cr(OH)4]
Cr(OH)2 + 2 HCl CrCl2 + 2 H2O
B

2 CrCl2 + 4 NaCH3COO + 2 H2O [Cr(CH3COO)2(H2O)] 2 + 4 NaCl

D

b. Xem phn l thuyt)

2.3. Phc cht crom (III)
Do c kch thc b v in tch ln nn ion Cr3+ c kh nng to phc rt mnh, cc phc bn thng
gp l [CrX6]3 (X: F, Cl, SCN, CN), [Cr(C2O4)2] , NH4[Cr(NH3)2(SCN)4] (mui Reinecke c mu m).
Trong dung dch nc, mui CrCl3 tn ti 3 dng khc nhau:
[Cr(H2O)6]Cl3

[Cr(H2O)5Cl]Cl2

[Cr(H2O)4Cl2]Cl

tm

xanh nht

xanh thm

3 AgCl

2 AgCl

1 AgCl

Cu 2.4. Cc hp cht A, B, C c cng cng thc phn t CrCl3.6H2O. Trong dung dch nc tn ti
cn bng gia chng nh sau:
[Cr(H2O)6]Cl3

[Cr(H2O)5Cl]Cl2.H2O

(A)

(B)

[Cr(H2O)4Cl2]Cl.2H2O.
(C)

Trong mt th nghim ngi ta cho dung dch cha 0,32 gam CrCl3.6H2O i qua mt lp nha trao i
cation di dng H+. Cn 28,8 ml dung dch NaOH 0,125M chun ht lng H+ chuyn vo dung
dch.
(a) Gi tn cc phc cht A, B v C. Phc cht no c ng phn hnh hc?
(b) Xc nh cng thc ca phc trong dung dch.
(c) Vit cu hnh electron ca Cr trong ion phc xc nh c (b) v xc nh t tnh ca phc cht
.
(a. A: Hexaaquacrom (III) clorua
B: Cloro pentaaqua crom (III) clorua hirat
Trang 10

C: icloro tetraaqua crom (III) clorua hirat (C ng phn hnh hc)

b. [Cr(H2O)6 nCln]Cl3 n.nH2O [Cr(H2O)6 nCln]3 n + (3 n) Cl + n H2O
1,20.10 3
[Cr(H2O)6 nCln]

3 n

1,20.10 3

mol

+ (3 n) R COOH ... + (3 n) H+

1,20.10 3

1,20.10 3 (3 n) mol

H+ + OH H2O
3,60.10 3 mol
C: nH+ = 1,20.10 3 (3 n) = 3,60.10 3
=> n = 0;
Vy phc trong dung dch l [Cr(H2O)6]Cl3 (phc A)
c. Phc thun t; 3(3 2) 3,87 M.B
3d

4s

4p
sp3d2

4d

[Cr(H2O)6]3+

6 H2 O

Cu 2.5. Thm t amoni dicromat vo mui amoni thioxianat nng chy s thu c mui Reinecke c
cng thc NH4[Cr(SCN)x(NH3)y], mui ny c thnh phn % theo khi lng ca cc nguyn t nh sau: Cr
15,5 %; S 38,15 % v N 29,2 %.
(a) Hy xc nh cc gi tr x v y trong cng thc trn.
(b) Hy xc nh s oxi ha ca crom trong phc.
(c) Hy cho bit hnh hc ca anion phc.
(d) Hy v cc ng phn lp th ca anion phc trn.
(a. NH4[Cr(SCN)4(NH3)2];
b. +3;
c. bt din;
d. ng phn hnh hc

NH3
NCS

Cr

NCS

SCN
SCN

NH3

NH3
NCS

Cr

NCS

SCN
NH3

SCN

Cu 2.6. Ion glyxinat, NH2CH2COO, l mt phi t hai cng, to phc trisglyxinatocrom(III). Lu

rng cc nguyn t oxi v nit ca cng mt phi t ch c th lin kt cc v tr cnh nhau trong cu hnh
bt din.
(a) Hy cho bit phc trn c bao nhiu ng phn hnh hc?
(b) Hy cho bit ng phn hnh hc no l bt i?
Trang 11

Mt phc cht khc ca crom c thnh phn % theo khi lng ca cc nguyn t nh sau: 19,5 % Cr;
40,0 % Cl, 4,5 % H v 36,0 % O. Ha tan 0,533 g phc vo 100 ml nc v thm tip 10 ml dung dch
HNO3 2 M. Thm lng d dung dch bc nitrat. Lc, ra kt ta v em sy kh thu c 0,287 g cht rn.
Mt khc un nng nh 1,06 g phc 100 C thy thot ra 0,144 g nc.
Nhit ng c ca dung dch thu c khi ha tan 1,33 g phc vo 100ml nc l 0,18 C. (Hng
s nghim lnh ca nc l 1,82 K.kg.mol 1).
(c) Hy cho bit cng thc ca phc.
(d) Hy v tt c cc ng phn lp th ca phc trn.
(a. Hai ng phn hnh hc (fac v mer).
O

N
N

N
bt i

N
Cr

Cr

O
N
bt i

b. C hai ng phn hnh hc u bt i.

c. Gi CTPT ca phc l CrxClyHzOt. C:
x: y : z :t

19,5 40,0 4,5 36,0

:
:
:
0,375 : 1,128 : 4,46 : 2,25 1 : 3 : 12 : 6
52,0 35,45 1,01 16,0

=> CTPT ca phc l CrCl3(H2O)6. (M = 266,47)

Th nghim 1:
[Cr(H2O)6 nCln]Cl3 n.nH2O [Cr(H2O)6 nCln]3 n + (3 n) Cl + n H2O
2,00.10 3

2,00.10 3(3 n) mol

Ag+ + Cl AgCl
2,00.10 3

mol

C: nAgCl = 2,00.10 3(3 n) = 2,00.10 3

=> n = 2
Th nghim 2:
[Cr(H2O)6 nCln]Cl3 n.nH2O [Cr(H2O)6 nCln]Cl3 n + n H2O
3,98.10 3

7,99.10 3

mol

C: nH2O = 3,98.10 3n = 7,99.10 3

=> n = 2
Th nghim 3:
[Cr(H2O)6 nCln]Cl3 n.nH2O [Cr(H2O)6 nCln]3 n + (3 n) Cl + n H2O
4,99.10 3
C: t km k

4,99.10 3

4,99.10 3 (3 n) mol

nion
mdm

(Coi lng nc do phc phn li ra khng ng k)

Trang 12

=> nion

tmdm
0,18K 0,1kg

9,89.10 3 mol
1
k
1,82 K .kg.mol

C: nion = 4,99.10 3 + 4,99.10 3 (3 n) = 9,89.10 3

=> n = 2
Kt qu ca 3 th nghim ph hp vi nhau, vy cng thc ca phc l [Cr(H2O)4Cl2]Cl.2H2O;
d. 2 ng phn hnh hc)
Cu 2.7. (a) Hy v v gi tn cc ng phn lin kt v ng phn lp th ca mi hp cht phi tr
sau:
i. [Pt(NH3)2(SCN)2].
ii. [Co(en)(H2NCH2COO)2]Cl.
(b) Hy v gin phn tch mc nng lng ca cc obitan d trong trng tinh th ca mi phc sau.
i. [Cr(CN)6]3 .
ii. [Cr(NH3)6]2+.
iii. [Cr(CN)6]4 .
(a. i.
NH3

NH3
NCS

NCS

SCN

Pt

NCS

SCN

Pt

NH3

NH3

SCN

NH3

NH3

Pt

NCS

NCS

Pt

NH3

NH3

NCS

NH3

NH3

Pt

SCN

NCS

Pt

NH3

NCS

NH3

ii.
N
O

Co
O

O
N

O
N

Co

Co
N

N
N

O
N

Co

Co

O
N

N
O

N
Co

N
O

b.

[Cr(CN)6]3-

[Cr(CN)6]4-

[Cr(NH3)6]2+ )

Trang 13

Cu 2.8. Phc kali xiano K1 ca nguyn t A c momen t = 3,8 B.M. Hp cht c cc i hp th

tng ng vi bc chuyn d d ti 26700 cm 1. Phn ng kh ion A2O72 (c mu da cam) bng etanol
trong mi trng axit to ra ion trung tm ca phc xiano. Phc K1 b kh bi kali trong amoniac lng cho
phc xiano K2 (c s phi tr khng thay i). Bng cch thay i tt c phi t trong K2 bng amoniac,
momen t ca phc K3 thu c tng ln thnh = 4,9 B.M..
(a) Hy cho bit A l nguyn t no?
(b) Hy cho bit cng thc v gi tn phc K1.
(c) Hy biu din s phn b ca electron trn cc obitan d ca nguyn t trung tm trong phc K1.
Cho NA = 6,0221023 mol 1; c = 3,0108 m/s v h = 6,6210 34 J.s.
(d) Hy tnh nng lng tch ca trng phi t (theo kJ/mol) ca phc K1.
(e) Cho cc phi t H2O, Cl v F cc gi tr nng lng tch: 158 kJ/mol, 182 kJ/mol v 208 kJ/mol.
Hy
cho
bit
nng
lng
tch
tng
ng
vi
mi
phi t.
(f) Hy cho bit cng thc v gi tn ca phc K2.
(g) Hy biu din s phn b ca electron trn cc obitan d ca nguyn t trung tm trong phc K 2 v
K3, v cho bit phc l spin cao hay spin thp?
(h) Phc K2 c cu trc bt din lch. Hy cho bit tn gi ca hiu ng gy ra iu ny.
(i) Hy cho bit hnh hc ca phc A(acac)2? Ch n hiu ng c cp phn (h).
(a. Cr;
b. K3[Cr(CN)6], kali hexaxiano cromat (III);
c.
; 3(3 2) 3,87B
d. E hc N A 6, 62.1034 J .s 3.108 m.s 1 26700cm1 100cm 6, 022.1023
m

319.103 J / mol 319kJ / mol

e. H2O: 208 kj/mol; Cl : 158 kj/mol; F : 182 kj/mol.
f. K4[Cr(CN)6], kali hexaxiano cromat (II);
g.

spin thp

spin cao

h. Hiu ng Jahn Teller;

i. Vung phng)
Cu 2.9. Trong cu hi ny cc phc ca Cr3+ v Cr2+ u c cu hnh bt din.

Trang 14

Thm amoniac vo dung dch Cr(III) to thnh Cr(OH)3, mt kt ta mu lc xm. Cr(OH)3 l hidroxit
lng tnh, phn ng vi axit to ion phc mu tm A, phn ng vi dung dch NaOH to ion phc mu
xanh thm B.
(a) Hy vit cng thc ca cc ion phc A v B.
(b) Hy vit phng trnh phn ng ca Cr(OH)3 vi axit v baz.
(c) Hy gii thch ti sao cc ion phc A v B li c mu khc nhau?
Ion phc A c tnh axit (pKa = 3,95). Baz lin hp ca A d dng b dime ha vi cu ni l ion hydroxo
a
to thnh ion phc X c cng thc [Cr2(OH)2(H2O)8] .
(d) Hy vit phn ng phn li axit ca A.
(e) Hy v cu trc khng gian v xc nh in tch a ca ion phc X.
C l phc triammintriclorocrom(III). Khi thm ion oxalat (ox) vo C th mt phi t Cl v mt phi t
NH3 s c thay th bng mt phi t ox to thnh ion phc D.
(f) Hy vit cng thc ca cc ion phc C v D.
(g) Hy v cc ng phn lp th ca C v D (s dng k hiu O

O cho

phi t oxalat).

Ion phc A b kh bng hn hng km thy ngn to thnh phc E mu xanh da tri rt km bn ca
Cr .
2+

(h) Hy v hai gin phn tch nng lng ca cc obitan d trong trng tinh th ca phc E.
(i) Hy tnh momen t ca phc E ng vi hai gin trn.
(k) Hy thit lp biu thc tnh nng lng lm bn trong trng tinh th ca E ng vi hai gin trn
theo nng lng tch (o) v nng lng ghp i electron (P).
(a. [Cr(H2O)6] 3+; [Cr(OH)6] 3 ;
b. Cr(OH)3 + 3 H3O+ [Cr(H2O)6] 3+
Cr(OH)3 + 3 OH [Cr(OH)6] 3
c. Do nng lng tch trong trng phi t ca hai phc khc nhau.
d. [Cr(H2O)6] 3+ + H2O

[Cr(OH)(H2O)5] 2+ + H3O+;

e.

f. C: [CrCl3(NH3)3]; D: [CrCl2(NH3)2ox] ;
g.

h.

Trang 15

i. 1 4(4 2) 4,9BM
2 2(2 2) 2,8BM

k. Elb1 3 2 o 3 o 3 o 6Dq ;
5

2
Elb 2 4 o Po 16 Dq Po )
5

Cu 2.10. Tinh th Ruby c mu m v c s dng lm trang sc. t ngi bit c rng

tri tim ca my pht tia laze u tin, c ch to bi Maiman vo nm 1960, l mt tinh th ruby ln.
Mu ca ruby l do s hp th nh sng ca ion Cr3+ c mt trong tinh th oxit nhm (Al2O3) khng
mu. Ion Cr3+ c 3 electron phn lp 3d v c kh nng hp th nh sng do s chuyn dch ca electron
gia cc obitan ca phn lp 3d c mc nng lng khc nhau.
(a) Hy cho bit ph hp th no di y l ph hp th ca ruby?

ng ruby dng trong my pht laze l mt ng hnh tr c chiu di 15,2 cm v c ng knh 1,15 cm.
Hm lng ion Cr3+ trong ng l 0,050 % theo khi lng. Khi lng ring ca Al2O3 l 4,05 g cm 3.
Nguyn t khi ca Cr = 52u.
(b) Hy tnh s ion Cr3+ c trong ng ruby.
Trong ruby ion Cr3+ c phi tr bi 6 ion oxit c cu hnh bt din. Hnh dng ca nm obitan 3d
c cho di y. Hnh tip theo l gin phn tch nng lng ca cc obian d thnh hai nhm, mt
nhm gm ba obitan c mc nng lng thp hn (t2g) v mt nhm gm hai obitan c mc nng lng cao
hn (eg).
(c) Hy cho bit nhng obitan 3d no (dz2, dxy, dyz, dx2 y2, dxz) thuc nhm t2g v nhng obian 3d no
thuc nhm eg?

Trang 16

eg

t2g

(d) Hy v gin phn tch mc nng lng ca cc obitan d trong trng tinh th ca phc Cr 3+
trong ruby.
Mt vin ruby c t trn mt chic cn n. Khi cn thng bng, ngi ta a mt cc nam chm
vo ngay pha di a cn ng vin ruby.

(e) Hy cho bit iu g s xy ra?

(A) Cc nam chm ko vin ruby xung.
(B) Cc nam chm khng lm vin ruby dch chuyn.
(C) Cc nam chm y vin ruby i ln.
(D) Cc nam chm lm cho vin ruby di chuyn ln xung.
(a. Ph s 4
2

0,05
1,15cm
3
15,2cm 3,14
4,05 gam.cm
100
2
b. N (Cr 3 )
6,022 .1023ion.mol 1 3,7.1020 ion
1
52 gam.mol

c. d.
dz2 dx2 - y2

dxy

dxz dyz

eg

t2g

e. A)
Cu 2.11. X l ion phc xianua ca crom c cu hnh bt din, tan trong nc v c tnh kh. Bit X c
momen t = 2,83 B.M.
(a) Hy xc nh s oxi ha ca crom trong X.
Thay th ton b phi t xianua trong X bng amoniac thu c phc Y. Bit X Y.
(b) Hy xc nh momen t (theo BM) ca Y.
Trang 17

(a. C: n(n 2) 2,83

=> n = 2,
Vy crom c s oxi ha +2 hoc +4 trong phc X.
Do X c tnh kh nn crom c s oxi ha +2. X: [Cr(CN)6] 4
d2sp3
[Cr(CN)6]46CN-

b. Y n(n 2) 4(4 2) 4,90BM

sp3d2
[Cr(NH3)6]2+

6 NH3

Cu 2.12. (a) Hy v cc ng phn ca cc phc sau:

i/ [Cr(NH3)4Cl2]Cl
ii/ [CoPy3Cl3], py l pyridin.
iii/ [Co(SCN)(H2O)5]Cl
iv/ [PtCl(PMe3)3]Br, Me l CH3.
v/ [Co(en)2Cl2]Cl.
(b) CrCl3 phn ng vi NH3 to thnh cc phc c cng thc chung l CrCl3(NH3)x (x = 3 6). Hy
vit cng thc ca cc phc trn v so snh dn in ca chng trong cc dung dch c cng nng .
(a. i/ [Cr(NH3)4Cl2]Cl: 2 ng phn (cis, trans).
Tetraammin dicloro crom (III) clorua
ii/ [CoPy3Cl3]: 2 ng phn (mer, fac).
Tricloro tris(pyridin) coban(III)
iii/ [Co(SCN)(H2O)5]Cl: 2 ng phn (lin kt).
Pentaaqua thioxianato coban(II) clorua
Pentaaqua isothioxianato coban(II) clorua
iv/ [PtCl(PMe3)3]Br: cu hnh vung phng, 2 ng phn (ng phn ion ha)
[PtCl(PMe3)3]Br: Cloro tris (trimetylphotphin)platin (II) bromua.
[PtBr(PMe3)3]Cl: Bromo tris (trimetylphotphin)platin (II) clorua.
v/ [Co(en)2Cl2]Cl: 3 ng phn (cis, trans).
Dicloro bis (etylendiamin)coban(III) clorua;
b. dn in: [Cr(NH3)6]Cl3 > [Cr(NH3)5Cl]Cl2 > [Cr(NH3)4Cl2]Cl > [Cr(NH3)3Cl3])

Trang 18

3. Phng php chun cromat

Phng php chun dicromat da trn kh nng oxi ho ca ion dicromat trong mi trng axit:
Cr2O72 + 14 H+ + 6e 2 Cr3+ + 7 H2O
Da cam

E0 = 1,33V

lc

u im:
K2Cr2O7 l cht gc.
khng phn ng vi Cl .
dung dch K2Cr2O7 bn theo thi gian, t b nh hng bi cht hu c.
Nhc im:
khng t ch th (do cng mu ca Cr2O72 khng ln).
phn ng tng i chm.
ng dng:
Xc nh cht kh: H2O2, S2O32 , Fe2+, SO32 , I , ru etylic, RSH, vitamin C, COD.
Xc nh cht oxi ho (chun ngc): Fe3+, NO3 , Cu2+, MnO4 , IO3 .
Xc nh cht khng c tnh oxi ha kh: Pb2+, Ba2+ (kt ta di dng MCrO4).
Cu 3.1. Ly 10 ml mu dung dch cha Cr(III) cho vo bnh nn, thm 5 ml dung dch H 2SO4 3M, 5
ml H3PO4 2M, 5 git dung dch AgNO3 1% v 1 git dung dch MnSO4 1%. Pha long dung dch bng nc
ct ti khong 100 ml. un trn bp in, cho tng lng nh mui (NH4)2S2O8 vo, lc dung dch lin tc,
khi dung dch c mu hng (mu ca Cr2O72 v MnO4 ) th dng cho pesunfat. Tip tc un si k cho
pesunphat phn hy ht. Thm tng git dung dch HCl 6M vo cho ti khi dung dch mt mu hng v
chyn sang mu vng da cam th ngng li. un tip 5 pht na ui ht Cl2 ra khi dung dch. ngui,
thm 5 ml H3PO4 2M, vi git cht ch th diphenyl amin, chun dung dch thu c bng dung dch Fe2+
0,032M ti khi dung dch chuyn t mu tm sang mu xanh nht thy ht 6,75 ml.
(a) Vit cc phng trnh phn ng xy ra trong th nghim.
(b) Cho bit vai tr ca AgNO3 v MnSO4 thm vo.
(c) Tnh nng ca Cr (III) trong dung dch mu.
(d) Nu S2O82 khng b phn hu ht th phng php mc sai s dng hay sai s m.
(a. 2Cr3+ + 3S2O82 + 7H2O Cr2O72 + 6SO42 + 14H+
2Mn2+ + 5S2O82 + 8H2O 2MnO4 + 10SO42 + 16H+
2S2O82 + 2H2O 4SO42 + O2 + 4H+
2MnO4 + 10Cl + 16H+ 2Mn2+ + 5Cl2 + 8H2O
Cr2O72 + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O
b. AgNO3: xc tc; MnSO4: ch th
c. 0,0072M)
Cu 3.2. Dung dch Cr2O72 trong mi trng axit c th oxi ho c etanol v etanal thnh axit etanoic
(axit axetic) v ion dicromat b kh thnh Cr(III). Dung dch AgNO3/ NH3 ch oxi ho c etanal, khng
oxi ho c etanol. Trong qu trnh ny, ion Ag+ b kh thnh bc kim loi.
Trang 19

C 500,0 ml dung dch cha etanol v etanal. xc nh nng ca mi cht, u tin ngi ta tin
hnh chun ho dung dch K2Cr2O7 trong mi trng axit bng cch chun vi dung dch FeSO4 (ion
icromat oxi ho Fe2+ thnh Fe3+). Chun b dung dch chun Fe2+ bng cch ho tan 7,43 gam FeSO4.7H2O
(MW= 287,0) vo bnh nh mc 100,0 ml v nh mc n vch bng nc ct deion. Chun 25,0 ml
dung dch ny thy ht 23,12 ml dung dch dicromat. Tip , chun 50,0 ml dung dch mu cha etanol
v etanal thy ht 22,45 ml dung dch dicromat. Trong mt th nghim khc, thm lng d dung dch
AgNO3/ NH3 vo 50,0 ml dung dch mu thy c 0,234 gam Ag to thnh.
(a) Vit cc phng trnh phn ng xy ra trong quy trnh.
(b) Ti sao phi axit ho dung dch dicromat?
(c) Tnh nng mol ca dung dch dicromat?
(d) Tnh nng ca etanol v etanal trong dung dch mu.
(a. 2Cr2O72 + 3C2H5OH + 16H+ 4Cr3+ + 3CH3COOH + 11H2O.
Cr2O72 + 3CH3CHO + 8H+ 2Cr3+ + 3CH3COOH + 4H2O
Cr2O72 + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O
2Ag+ + CH3CHO + H2O 2Ag + CH3COOH + 2H+
b. Trong mi trng trung tnh hoc kim, tnh oxi ho ca Cr2O72 yu hn trong mi trng axit. Mt
khc, trong mi trng trung tnh, sn phm kh l Cr(OH)3 khng tan
c. Fe2+: 0,259M; Cr2O72 : 0,0467M
d. C2H5OH: 0,716M; CH3CHO: 0,0217M)
Cu 3.3. Hm lng Fe2O3 trong qung hematit c xc nh bng phng php chun oxi ha
kh. Trong mt th nghim, 4,00 g bt hematit c x l bng dung dch axit clohidric c. Phn khng tan
c lc b, kh ton b ion st trong phn dung dch thnh Fe2+. Chun dung dch thu c ( pH = 0)
bng dung dch dicromat 0,100 mol/lit). Th tch dung dch cn t ti im tng ng l 33,74 ml.
(a) Hy vit phng trnh phn ng ca st (III) oxit vi axit clohidric.
(b) Hy chn nhng cht kh thch hp trong s cc cht kh cho di y kh Fe(III) thnh Fe(II):
bromua, nitrit, sunphit, hn hng km thy ngn v Sn2+.
Cho th kh chun ca mt s cp oxi ha kh lin hp nh sau:
Cp oxi ha/ kh
2+

0,76

Zn /Zn
4+

E (V)

2+

Sn /Sn

2
2
SO4 /SO3

0,15
0,17

Cp oxi ha/ kh
3+

Fe /Fe

2+

2
3+
Cr2O7 /Cr

Cl2/Cl

E (V)
0,77
1,33
1,36

Cp oxi ha/ kh

BrO3 /Br
3+

Mn /Mn

E (V)
1,44

2+

1,51
2+

MnO4 /Mn

1,51

(c) Hy vit phng trnh phn ng chun v tnh hng s cn bng ca phn ng.
(d) Hy tnh thnh phn % theo khi lng ca Fe2O3 c trong mu hematit.
(e) Hy tnh th ca dung dch ti im tng ng trong php chun trn.
(g) Hy chn nhng cht ch th oxi ha kh thch hp cho php chun trn t cc cht ch th cho
di y.
st phenantrolin (xanh nht/ E = 1,14V).
ferroin (xanh/ da cam E = 1,06V).
indigocamin (xanh/ vng E = 0,29V).
Trang 20

 metylen xanh (xanh/ khng mu E = 0,53V).

nilblue sunphat (tm/ khng mu E = 0,41V).
(h) Hy cho bit ion clorua c b oxi ha trong qu trnh chun khng?
Mt phng php khc nh lng st (II) l phng php chun kali pemanganat. trnh to
thnh clo ngi ta thm vo dung dch st (II) 10,0 ml dung dch bo v. Dung dch ny cha MnSO4, axit
sunfuric v axit photphoric c.
(i) Hy tnh gi tr pH ti thiu ti ion clorua b oxi ha thnh clo bi pemanganat. Bit nng ca
tt c cc ion khc u l 1 M.
(j) Hy cho bit th kh ca cp MnO4 , H+/ Mn2+ thay i nh th no khi thm MnSO4 vo dung
dch?
(k) Hy cho bit vai tr ca axit photphoric trong dung dch bo v?
(a. Fe2O3 + 6 HCl 2 FeCl3 + 3 H2O
b. Cht kh thch hp: Zn, Sn2+, SO32 ; do chng c E < 0,77 V;
2+

c. 6 Fe

Cr2O72

+ 14 H 6 Fe
+

3+

+ 2 Cr

3+

+ 7 H2O

K 10

6 (1, 33 0, 77)
0, 0592

5,7.1056

d. 40,5%
e. Ti im tng ng
3
3

[ Fe ] 3[Cr ]
2
2

[ Fe ] 6[Cr2O7 ]

C:

0
E EFe
0,0592 log
3
/ Fe 2

0
E ECr

O 2 / 2Cr3
2 7

=>

[ Fe 3 ]
[ Fe 2 ]

0,0592
[Cr O 2 ][ H ]14
log 2 7 3 2
6
[Cr ]

0
7 E EFe
0,0592 log
3
/ Fe 2

[ Fe 3 ]
[Cr2O72 ][ H ]14
0

6
E

0
,
0592
log
2

Cr2O7 / 2Cr
[ Fe 2 ]
[Cr 3 ]2

0
0
EFe
6 ECr
0,0592 log
3
/ Fe 2
O2 / 2Cr3
2 7

0
0
EFe
6 ECr
0,0592 log
3
/ Fe 2
O 2 / 2Cr3
2 7

[Cr2O72 ][ H ]14 3[Cr 3 ]

[Cr 3 ]2 6[Cr2O72 ]

0
0
EFe
6 ECr
0,0592 log
3
/ Fe 2
O 2 / 2Cr3
2 7

=>

[Cr2O72 ][ H ]14[ Fe 3 ]
[Cr 3 ]2 [ Fe 2 ]

[ H ]14
2[Cr 3 ]

0
0
EFe
6 ECr
0,0592 log
3
/ Fe 2
O 2 / 2Cr3
2 7

[ H ]14
2[Cr 3 ]

0
0
EFe
6 ECr
3
/ Fe 2
O 2 / 2 Cr3
2 7

1,25V

g. Cht ch th thch hp: st phenantrolin, ferroin; do E ca cht ch th nm trong khong bc nhy

th ca ng cong chun .
h. Khng v E(Cl2/Cl ) > E(Cr2O72 /Cr3+);

Trang 21

i. 1,36 1,51

0,0592
1 [ H ]8
;
log
5
1

pH = 1,58;
j. gim
k. to phc vi Fe3+; Fe(PO4)23 )
Cu 3.4. Quy trnh phn tch crom trong mu thp khng g cha Fe, Cr v Mn.
Pha dung dch chun FeSO4: Ho tan 9,9823 gam mui Mohr (FeSO4.(NH4)2SO4.6H2O) vo bnh nh
mc 250 ml c H2SO4 v nh mc n vch bng nc ct.
(a) Tnh nng mol ca dung dch FeSO4 thu c.
Chun ho dung dch KMnO4: Ly 25,0 ml dung dch FeSO4 va pha ch trn cho vo bnh nn, thm
1 ml dung dch H3PO4 c ( to phc khng mu vi Fe3+), chun dung dch thu c bng dung dch
KMnO4 thy va ht 24,64 ml.
(b) Tnh nng mol ca dung dch KMnO4.
Chun b mu: Ho tan 0,2800 gam mu thp trong dung dch hn hp H3PO4 v H2SO4 c, un nng
cho
n
khi
thu
c
dung
dch
trong
sut
mu
xanh.
3+
3+
2+
(Fe Fe , Cr Cr , Mn Mn ). Lm lnh dung dch n nhit phng. Thm 5 ml dung dch
AgNO3 1%, 20 ml dung dch (NH4)2S2O8 20%. Sau vi pht dung dch c mu hng (pesunfat oxi ho Mn2+
thnh MnO4 , Cr3+ thnh Cr2O72 , Ag+ ng vai tr lm cht xc tc). un si dung dch phn hu ht
ion pesunfat cn d (sinh ra SO42 v O2). Thm t t tng git HCl c n khi dung dch chuyn t mu
hng sang mu vng (HCl phn ng chn lc vi MnO4 ). Sau khi kt thc qu trnh thy c kt ta trng
xut hin y bnh.
(c) Vit phng trnh phn ng ca Cr3+, Mn2+ vi S2O82 trong mi trng axit.
(d) Vit phng trnh phn ng loi MnO4 bng dung dch HCl c.
(e) Hy cho bit kt ta trng l cht g? c to thnh nh th no?
Tin hnh chun : Chuyn dung dch thu c trn vo bnh nh mc 250 ml ri nh mc n
vch bng nc ct (dung dch A). Ly 50 ml dung dch A cho vo bnh nn, thm tip 25,0 ml dung dch
FeSO4. Lng FeSO4 d c chun bng dung dch KMnO4 thy va ht 19,89 ml.
(g) Vit phng trnh phn ng ca Fe2+ vi Cr2O72 .
(h) Tnh % khi lng ca Cr trong mu thp (Cr = 52,0).
(a. 0,1019 M;
b. 0,02068 M;
c. 2 Cr3+ + 3 S2O82 + 7 H2O Cr2O72 + 6 SO42 + 14 H+
2 Mn2+ + 5 S2O82 + 8 H2O 2 MnO4 + 10 SO42 + 16 H+
d. 2 MnO4 + 10 Cl + 16 H+ 2 Mn2+ + 5 Cl2 + 8 H2O
e. AgCl;
h. 15,19%)
Cu 3.5. Crom c iu ch t qung FeCr2O4, st c tch ra khi qung theo hai bc:
4 FeCr2O4 + 8 Na2CO3 + 7 O2 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
Trang 22

2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O

Kh icromat bng cacbon s thu c crom(III) oxit, kh oxit to thnh bng phng php nhit nhm
s thu c crom.
Na2Cr2O7 + 2 C Cr2O3 + Na2CO3 + CO
Cr2O3 + 2 Al Al2O3 + 2 Cr
(a) Hy tnh khi lng crom c to thnh t 2,1 tn qung c cha 72,0% FeCr2O4 (Cr = 52,00; Fe
= 55,85; O = 16,00). Gi thit hiu sut ca c qu trnh l 100%.
Mt mu thp c cha Mn v Cr. Mn v Cr trong 5,00 gam mu thp c oxi ha thnh MnO 4 v
Cr2O72 v pha long thnh 100,0 ml dung dch. Ly 50,0 ml dung dch, thm BaCl2 n d v iu chnh
pH n gi tr thch hp, cromat kt ta hon ton v thu c 5,82 g BaCrO4. 50,0 ml dung dch cn li
phn ng va vi 43,5 ml dung dch Fe2+ 1,60 M trong mi trng axit.
MnO4 + Fe2+ + H+ Mn2+ + Fe3+
Cr2O72 + Fe2+ + H+ Cr3+ + Fe3+
(b) Hy tnh thnh phn % theo khi lng ca Mn v Cr trong mu thp (Mn = 54,94; Ba = 137,33).
(a. S hp thc: FeCr2O4 2 Cr; mCr = 702 kg;
b.

MnO4 + 5 Fe2+ + 8 H+ Mn2+ + 5 Fe3+ + 4 H2O

Cr2O72 + 6 Fe2+ + 14 H+ 2 Cr3+ + 6 Fe3+ + 7 H2O

Cr: 47,8%; Mn: 0,3%)

Cu 3.6. Hm lng crom trong mt mu thp khng g (cha Fe Cr) c xc nh theo quy trnh
sau:
1. Ha tan 0,1000 g mu thp bng 20 ml dung dch axit sunfuric 1,8 M, un nng.
2. Thm tip 4 ml dung dch axit nitric c v un khong 10 pht cho n khi dung dch chuyn t
mu xanh sang mu lc.
3. Thm 10 ml dung dch bc nitrat 0,5% v 6 g amoni pesunfat ((NH4)2S2O8). un si dung dch
khong 20 pht amoni sunfat b phn hy hon ton, dung dch thu c c mu da cam.
4. Thm 10 ml dung dch NaCl 5%.
5. Thm chnh xc 20,00 ml dung dch FeSO4(NH4)2SO4 1,0010 1 mol lit 1.
6. Chun dung dch thu c bng dung dch KMnO4 2,00 10 2 mol lit 1.
(a) Hy vit cc phng trnh phn ng xy ra bc 2.
(b) Hy vit phng trnh phn ng xy ra bc 3.
(c) Hy vit phng trnh phn ng xy ra bc 4 v cho bit mc ch ca qu trnh.
(d) Hy vit phng trnh phn ng xy ra bc 5. Hy cho bit mu ca dung dch thu c.
(e) Hy vit phng trnh phn ng xy ra bc 6.
(f) Php chun bc 6 cn 12,00 ml dung dch pemanganat t ti im tng ng. Hy tnh
thnh phn % theo khi lng ca crom c trong mu thp.
(a. Fe2+ + 2 H+ + NO3 Fe3+ + NO2 + H2O
Cr2+ + 2 H+ + NO3 Cr3+ + NO2 + H2O
Trang 23

lc

xanh
b. 2 Cr

3+

+ 3 S2O8

+ 7 H2O Cr2O72 + 6 SO42 + 14 H+

c. Ag+ + Cl AgCl
Mc ch: loi Ag+ ra khi dung dch, ngn cn qu trnh Cr3+ b oxi ha tr li thnh Cr2O72 bc
sau trong trng hp amoni pesunfat khng b phn hy ht;
d. 6 Fe2+ + Cr2O72 + 14 H+ 6 Fe3+ + 2 Cr3+ + 7 H2O
0,8

0,8/6 mmol

dung dch chuyn t mu da cam sang mu lc ca Cr3+.

e. 5 Fe2+ + MnO4 + 8 H+ 5 Fe3+ + Mn2+ + 4 H2O
1,2

0,24 mmol

f. Tng s mmol Fe2+ a vo dung dch l: 20 0,1 = 2 mmol;

=> nCr = 1,6/6 mmol;

1,6
52
6
100 13,87% )
=> %Cr
100
Cu 3.7. xc nh hm lng ca crom v st trong mt mu gm Cr2O3 v Fe2O3, ngi ta un
nng chy 1,98 gam mu vi Na2O2 oxi ha Cr2O3 thnh CrO42 . Cho khi nung chy vo nc, un
si phn hu ht Na2O2. Thm H2SO4 long n d vo hn hp thu c v pha thnh 100,00 ml, c
dung dch A c mu vng da cam. Cho dung dch KI (d) vo 10,00 ml dung dch A, lng I3 (sn phm
ca phn ng gia I v I2) gii phng ra phn ng ht vi 10,50 ml dung dch Na2S2O3 0,40 M. Nu cho
dung dch NaF (d) vo 10,00 ml dung dch A ri nh tip dung dch KI n d th lng I3 gii phng ra
ch phn ng ht vi 7,50 ml dung dch Na2S2O3 0,40 M.
(a) Vit cc phng trnh phn ng xy ra.
(b) Gii thch vai tr ca dung dch NaF.
(c) Tnh thnh phn % khi lng ca crom v st trong mu ban u. Cho: Fe = 56; Cr = 52.
(a. Cr2O3 + 3 Na2O2 2 Na2CrO4 + Na2O

(1)

2 Na2O2 + 2 H2O O2 + 4 OH + 4 Na+

(2)

OH + H+ H2O

(3)

2 CrO42 + 2 H+ Cr2O72 + H2O

(4)

Fe2O3 + 6 H+ 2 Fe3+ + 3 H2O

(5)

Cr2O72 + 9 I + 14 H+ 2 Cr3+ + 3 I3 + 7 H2O

(6)

2 Fe3+ + 3 I 2 Fe2+ + I3

(7)

S2O32
3+

Fe

+ I3

+ 3F

S4O6

+ 3I

FeF3

(8)
(9)

b. Vai tr ca dung dch NaF: F c mt trong dung dch to phc bn, khng mu vi Fe3+, dng
che Fe3+.
c. Trong 10 ml dung dch A: Cr2O72 : x mol; Fe3+: y mol.
3x + y/2 = 4,2.10 3/2
Trang 24

3x = 3.10 3/2
x = 5.10 4; y = 1,2.10 3
%Fe = 33,94%; %Cr = 26,27%)
Cu 3.8. Ha tan hon ton 1500 mg mt mu hp kim cha bc, ng v crom thnh 500,00 ml dung
dch
cha
Ag+,
Cu2+
v
Cr3+
(dung
dch
A).
Ly
50,00 ml dung dch A tin thnh theo quy trnh sau:
Sau khi tch bc v ng, ion crom (III) c oxi ha theo phn ng sau:
OH + Cr3+ + H2O2 CrO42 + H2O
Thm 25,00 ml dung dch Fe2+ 0,100 M. Phn ng xy ra nh sau:
H+ + Fe2+ + CrO42 Fe3+ + Cr3+ + H2O
phn ng vi lng Fe2+ d cn dng va 17,20 ml dung dch KMnO4 0,020 M. Phn ng xy ra
nh sau:
H+ + Fe2+ + MnO4 Fe3+ + Mn2+ + H2O
Trong mt th nghim khc, ly 200 ml dung dch A em in phn. C ba kim loi b kt ta hon ton
sau khi in phn 14,50 pht vi cng dng 2A. Bit hiu sut ca qu trnh in phn l 90%.
Hy vit cc phng trnh phn ng xy ra v tnh thnh phn % theo khi lng ca mi kim loi
trong hp kim u. Cu = 63,55; Ag = 107,87; Cr = 52,00.
(t s mol Ag, Cu v Cr trong 1500 mg mu hp kim ban u ln lt l x, y v z. C:
107,87x + 63,55y + 52,00z = 1,5
10 OH

+ 2 Cr

3+

+ 3 H2O2 2

z/10

(1)
CrO42

+ 8 H2O

z/10

8 H+ + 3 Fe2+ + CrO42 3 Fe3+ + Cr3+ + 4 H2O

3z/10

z/10

8 H+ + 5 Fe2+ + MnO4 5 Fe3+ + Mn2+ + 4 H2O

C: nFe 2

3z
3z
5nMnO
5 0,0172 0,02 0,025 0,1
4
10
10

(2)

Qu trnh in phn:
Ag+ + e Ag
2x/5

2x/5

Cu2+ + 2e Cu
2y/5

4y/5

Cr3+ + 3e Cr
2z/5
C: ne

6z/5

2x 4 y 6z
2 14,5 60
0,9
0,01623
5
96485

(3)

T (1), (2) v (3) suy ra:

x = 4,25.10 3 mol; y = 1,43.10 2 mol; z = 2,6.10 3 mol
Trang 25

=>

%Ag = 30,56%;

% Cu = 60,58%; % Cr = 8,86%)

Cu 3.9. Trong mt nh my ha cht iu ch fomandehit bng phn ng oxi ha metanol, dung dch
cha metanol v fomandehit c em phn tch. kim tra phng php ngi ta tin hnh th nghim
vi dung dch chun cha metanol v fomandehit. Cc dung dch c s dng nh sau:
Metanol, 5,00 g/lit
Fomandehit, 5,00 g/lit
Kali dicromat, 3,000.10 2 mol/lit
Amoni st(II) sunphat, 0,2000 mol/lit
Iot, 0,1000 mol/ lit
Natri thiosunfat, 0,2000 mol/lit
I. Trn 10,00 ml dung dch metanol vi 100,00 ml dung dch kali dicromat, thm khong 100 ml dung
dch axit sunfuric c v yn khong 30 pht. Lng dicromat d c chun bng dung dch Fe 2+ vi
cht ch th axit diphenylamin sunphonic (mu i t tm sang xanh nht). Th tch dung dch Fe2+ cn
dng t ti im tng ng l 43,5 ml.
II. Trn 10,00 ml dung dch fomandehit vi 50,00 ml dung dch iot. Thm dung dch NaOH cho ti khi
dung dch c mi trng kim v yn khong 10 pht. Thm axit clohidric trung ha dung dch, lng
iot d c chun bng dung dch thiosunphat, vi cht ch th h tinh bt. Th tch dung dch thiosunfat cn
dng t ti im tng ng l 33,3 ml.
(a) Hy tnh t l s mol metanol/icromat v fomandehit /iot tham gia phn ng vi nhau.
(b) Hy vit phng trnh phn ng ca metanol vi icromat trong mi trng axit v ca fomandehit
vi iot trong mi trng kim.
III. Bit rng iot khng phn ng vi metanol. Ly hai mu dung dch cha metanol v fomandehit cha
bit nng , mi mu c th tch 10,00 ml.
Mt mu c trn vi 100,00 ml dung dch kali dicromat v axit sunfuric c nh trong th nghim I.
Lng dicromat d phn ng va vi 4,8 ml dung dch Fe2+.
Mu cn li c trn vi 50,00 ml dung dch iot v c tin hnh nh th nghim II. Lng iot d
phn ng va vi 16,50 ml dung dch thiosunfat.
(c) Hy vit cc phng trnh phn ng xy ra v tnh nng (theo g/lit) ca metanol v fomandehit
trong dung dch.
(a. Th nghim I:
CH3OH + K2Cr2O7 ...
6 Fe2+ + Cr2O72 + 14 H+ 6 Fe3+ + 2 Cr3+ + 7 H2O
S mol metanol c trong 10,00 ml dung dch l:

nCH3OH

0,01 5
1,56.103 mol
32

S mol K2Cr2O7 phn ng vi metanol l:

nK Cr O 0,1 0,03
2

0,0435 0,2
1,55.103 mol
6
Trang 26

nCH 3OH

=>

nK 2 Cr2 O7

1,56.103 1

1,55.10 3 1

Th nghim II:
HCHO + I2 ...
I2 + 2 S2O32 2 I + S4O62
S mol fomandehit c trong 10,00 ml dung dch l:

0,01 5
1,67.103 mol
30

nHCHO

S mol I2 phn ng vi fomandehit l:

nI 2 0,05 0,1

0,0333 0,2
1,67.103 mol
2

=>

nHCHO 1,67.103 1

nI 2
1,67.103 1

b.

CH3OH + Cr2O72 + 8 H+

CO2 + 2 Cr3+ + 6 H2O

HCHO + I2 + 3 OH HCOO + 2 I + 2 H2O

c. t s mol ca CH3OH v HCHO c trong 10,00 ml dung dch mu ln lt l x v y.
CH3OH + Cr2O72 + 8 H+
x

CO2 + 2 Cr3+ + 6 H2O

3 HCHO + 2 Cr2O72 + 16 H+ 3 CO2 + 4 Cr3+ + 11 H2O

y

2y/3
+ Cr2O72 + 14 H+ 6 Fe3+ + 2 Cr3+ + 7 H2O

2+

6 Fe

C: nK Cr O x
2

2 y nFe 2
2y

x
1,6.10 4 0,1 0,03
3
6
3

(1)

HCHO + I2 + 3 OH HCOO + 2 I + 2 H2O

y

I2 + 2 S2O32 2 I + S4O62
C: nI 2 y

nS O 2
2

y 1,65.103 0,1 0,05

(2)

T (1) v (2) suy ra:

x = 6,07.10 4 mol; y = 3,35.10 3 mol
=> CCH3OH

CHCHO

6,07.104 mol.l 1 32 gam.mol 1

1,94 gam / lit
0,01 lit

3,35.103 mol.l 1 30 gam.mol 1

10,05 gam / lit )

0,01 lit

Trang 27

Cu 3.10. Dung dch dicromat trong mi trng axit c th oxi ha etanol v etanal thnh axit etanoic,
v ion dicromat b kh thnh ion Cr(III). Dung dch bc (I) trong amoniac c th oxi ha etanal, nhng
khng phn ng vi etanol.
Dung dch X cha etanol v etanal cha bit nng . xc nh nng ca hai cht trong X, u
tin ngi ta tin hnh xc nh nng ca dung dch K2Cr2O7 c axit ha. Dung dch st (II) c
iu ch bng cch ha tan 7,43 g FeSO4.7H2O vo nc c 100,0 ml dung dch. 25,0 ml dung dch
ny phn ng va vi 23,12 ml dung dch dicromat t ti im tng ng.
Chun 50,0 ml dung dch X bng dung dch icromat trn thy va ht 22,45 ml dung dch t
ti im tng ng.
Thm lng d dung dch bc (I) nitrat trong amoniac vo 50,0 ml dung dch X thy to 0,234 g bc.
(a) Hy vit cc phng trnh ion rt gn ca cc phn ng xy ra.
(b) Hy gii thch ti sao li phi axit ha dung dch icromat?
(c) Hy tnh nng mol ca dung dch K2Cr2O7.
(d) Hy tnh nng mol ca etanol v etanal trong X.
(a. 3 C2H5OH + 2 Cr2O72 + 16 H+ 3 CH3COOH + 4 Cr3+ + 11 H2O
x

2x/3

3 CH3CHO + Cr2O72 + 8 H+ 3 CH3COOH + 2 Cr3+ + 4 H2O

y

y/3

CH3CHO + 2 Ag(NH3)2+ + H2O CH3COO + 3 NH4+ + NH3 + 2 Ag

y

2y

6 Fe2+ + Cr2O72 + 14 H+ 6 Fe3+ + 2 Cr3+ + 7 H2O

b. Axit ha phn ng xy ra hon ton, sn phm ca phn ng l Cr3+ ch khng phi kt ta
Cr(OH)3.
CFe 2

c. C:

=> CK Cr O
2

7,43
0,2672 M
278,05 0,1

0,2672 25

23,12

1
6 0,04815M

d. t s mol ca etanol v etanal trong 50,0 ml dung dch X ln lt l x v y. C:

nK

2 Cr2 O7

2x y
0,04815 0,02245 1,081.103 mol
3 3

nAg 2 y

0,234
2,169.103 mol
107,87

(1)
(2)

T (1) v (2) suy ra:

x = 1,079.10 3 mol; y = 1,085.10 3 mol;
=>

CC2 H 5OH

1,079.103
0,0216 mol / l
0,05

Trang 28

CCH3CHO

1,085.103
0,0217 mol / l )
0,05

Cu 3.11. Oxi trong khng kh oxi ha chm Fe(II) trong dung dch axit thnh st (III).
(a) Hy vit phng trnh phn ng oxi ha Fe2+ bng oxi.
(b) Hy cho bit pH ca dung dch nh hng th no n phn ng (a).
Kesan, mt nh ha hc tr, quyt nh nghin cu nh hng ca oxi khng kh n dung dch st (II)
peclorat. Kesan cn 13,4 gam mu Fe(ClO4)2.xH2O v ha tan vo nc to thnh 200,0 ml dung dch A.
Thuc th H3L, mt phi t hu c, phn ng hon ton vi ion Fe(III) theo phng trnh: Fe3+ + 2
H3L (aq) [FeL2]3 + 6 H+
Bit H3L c mu lc thm, phc [FeL2]3 c mu vng nht v H3L khng to phc vi ion st (II). Do
c th s dng H3L chun nh lng ion Fe(III) khi c mt ion Fe(II). Ti im tng ng dung
dch chuyn t mu vng nht sang mu lc nht.
Ly 20,0 ml dung dch A cho vo bnh nn. Tin hnh oxi ha hon ton st (II) thnh st (III) bng
lng d dung dch kali dicromat trong mi trng axit, ion Cr(III) sinh ra cng phn ng vi H 3L ging
nh ion Fe(III). Chun dung dch thu c bng dung dch H3L 0,3182 M thy cn dng 30,20 ml dung
dch t ti im tng ng.
(c) Hy cho bit s oxi ha ca crom trong kali icromat.
(d) Hy vit phng trnh ion rt gn ca phn ng oxi ha Fe(II) thnh st (III) bng icromat.
(e) Hy tnh nng mol ca Fe(II) trong dung dch A. Gi thit rng trong dung dch A khng c mt
Fe(III).
(g) Hy tnh gi tr ca x.
xc nh nh hng ca oxi khng kh n dung dch st (II) peclorat, Kesan ly hai mu dung dch A
u c th tch 20,0 ml cho vo hai bnh nn sch, k hiu l 1 v 2. Tin hnh chun ngay bnh nn 1 bng
dung
dch
H3L
0,3182
M,
kt qu cho thy mu lc bn xut hin ngay sau khi thm mt git dung dch thuc th. Bnh nn 2 c
ngoi khng kh trong vng 1 tun, sau tin hnh chun thy ht 11,35 ml dung dch H3L 0,3182 M
t ti im tng ng.
(h) Hy gii thch kt qu khi tin hnh th nghim vi bnh nn 1.
(i) Hy tnh nng mol ca Fe(III) trong bnh nn 2.
(k) Hy tnh % lng ion Fe(II) cn li trong bnh nn 2 so vi lng Fe(II) ban u.
(l) Nu bnh nn 2 c ngoi khng kh hai tun thay v mt tun, hy cho bit th tch dung dch
H3L cn dng t ti im tng ng s ln hn, nh hn hay bng 22,70 ml?
(a. O2 + 4 Fe2+ + 4 H+ 4 Fe3+ + 2 H2O
b. Vi iu kin Fe3+ v Fe2+ cha b thy phn th khi pH tng th hiu sut phn ng gim.
c. +6
d. 6 Fe2+ + Cr2O72 + 14 H+ 6 Fe3+ + 2 Cr3+ + 7 H2O
x

x/3

e. t s mol Fe2+ c trong 20,0 ml dung dch A l x.

Fe2+ + 2 H3L (aq) [FeL2] 3 + 6 H+
Trang 29

x
Cr

2x
3+

+ 2 H3L (aq) [CrL2] 3 + 6 H+

x/3

2x/3

C: nH 3 L 2 x

2x
0,03020 0,3182 9,610.103 mol
3

=> x = 3,604.10 3 mol

=> CFe 2

3,604.103
0,1802 M
0,0200

CFe 2

g. C:

13,4
254,75 18,02 x

0,180 2M
0,2

=> x = 6,52
h. Kt qu thc nghim chng t trong bnh nn 1 khng c mt Fe(III).
i. CFe 3

11,35 0,3182
20,0

k. %Fe(II) cn li

1
2 0,0903 M

0,1802 0,0903
100 49,89%
0,1802

l. Khi ton b lng Fe2+ b chuyn thnh Fe3+ th th tch dung dch H3L cn dng phn ng va
vi lng Fe3+ sinh ra l:
VH 3 L , max

0,1802 20,0 2
22,65 ml
0,3182

Vy sau hai tun th th tch dung dch H3L cn dng s nh hn 22,70 ml)
Cu
nh sau:

3.12.

Cho

gin

Latimer

ca

crom

trong

mi

trng

axit

(pH

0)

+0,293
Cr2O72- +0,55
da cam

Cr(V)

Cr(IV)
xanh

+2,1

[Cr(H2O)6]3+
tm

[Cr(H2O)6]2+
lc
-0,744

-0,912

Cr

(a) Hy tnh cc gi tr X

v Y trong gin trn.

(b) Hy cho bit Cr (IV) c b phn hy d ly thnh Cr (III) v Cr (VI) khng?
(c) Cp Cr2O72 /Cr3+ c s dng lm cht oxi ha. Hy vit bn phn ng ca cp trn.
(d) Hy tnh s thay i th ca cp trn nu pH ca dung dch tng t 1 n 3 (T = 298 K, E(Cr 2O72
/Cr3+) = 1,33 V). Bit trong khong pH ny nng ca Cr2O72 v Cr3+ coi nh khng thay i.
(e) Chun 100 ml dung dch kali dicromat 0,01667 M bng dung dch Fe(II) 0,1 M. Hy tnh th kh
ca dung dch thu c sau khi thm 100 ml dung dch Fe(II) 0,1 M. Bit trng thi cn bng c pH=1; E
(Fe3+ /Fe2+) = 0,77V.
Trong mt th nghim, mt bnh in phn cha 150 lit dung dch axit cromit H2CrO4. Qu trnh in
phn c thc hin trong khong thi gian 8 gi vi cng dng in 2000A. Vt cn m ng vai tr
Trang 30

l catot c ph 350g crom sau khi th nghim kt thc. Ti catot bn cnh crom kt ta cn xy ra phn
ng gii phng kh. Do hiu sut ca qu trnh in phn to crom nh hn 100%.
(g) Hy vit bn phn ng to crom catot v tnh hiu sut ca qu trnh in phn to crom.
(h) Hy vit cc bn phn ng to kh catot v anot v tnh th tch kh thot ra anot v catot 298
K v 1,013.105 N/m2.
(i) Mt loi thuc tr su cha ng (II) oleat Cu(C18H33O2)2 (M = 626). Cho 9,9 g mu thuc tr su
ny vo hn hp axit sunfuric v axit nitric c un nng ph hy ht phn hu c. Thm lng d kali
cromat vo dung dch thu c kt ta ng di dng mui cromat baz CuCrO4.2CuO.2H2O. Cht kt
ta c lc, ra v ha tan trong dung dch axit:
2 (CuCrO4.2CuO.2H2O) (r) + 10 H+ (aq.) 6 Cu2+(aq.) + Cr2O72 (aq.) + 9 H2O
Chun lng icromat sinh ra cn 15,7 ml dung dch Fe2+ 0,232 M. Hy tnh thnh phn % theo khi
lng ca ng (II) oleat c trong mu.
(a. C: 6 0,293 = 0,55 + x + 2,1 + 3 (0,744)
=>

x = 1,34 V

C: 3 (0,744) = y + 2 (0,912)
y = 0,408 V;

=>

b. 3 Cr(IV) 2 Cr(III) + Cr(VI)

0,55 1,34
0,945V
2

0
C: ECr

O 2 / Cr ( IV )
2

Cch 1: K 10

2( 2,1 0, 945)
0, 0592

1,05 .1039

Cch 2: G0 = nFE0pin = 2 96485 (2,1 0,945) = 222,88 kJ/mol < 0.

Vy Cr(IV) t phn hy d ly to Cr(III) v Cr(VI).
c. Cr2O72 + 14 H+ + 6 e 2 Cr3+ + 7 H2O
d. pH = 1:
0
ECr O 2 / Cr 3 ECr

O 2 / Cr 3
2

0,0592 [Cr2O72 ][ H ]14

0,0592
lg
1,33
lg(101 )14 1,19V
3 2
6
[Cr ]
6

pH = 3:
0
ECr O 2 / Cr 3 ECr

O 2 / Cr 3
2

0,0592 [Cr2O72 ][ H ]14

0,0592
lg
1,33
lg(103 )14 0,92V
3 2
6
[Cr ]
6

Vy khi pH tng t 1 n 3 th th kh ca h gim 0,27V;

e.

Cr2O72

2+

+ 6 Fe

b: 8,335

50

8,335

50

cb

C: K

+ 14 H

2 Cr

3+

+ 6 Fe

+ 7 H2O

K 10

6(1, 33 0, 77)
0, 0592

5,71.1056

mM
16,67

0,1

3 2

3 6

2
7

[Cr2O ] (6[Cr2O ]) 0,1

6

50

16,67

16,67.10 50,00.10
2
7

3+

14

50

mM
mM

5,71.1056

Trang 31

[Cr2O72 ] = 3,997.10 9 M

=>
=> Edd ECr O

2
2 7

/ Cr 3

0
ECr

O 2 / Cr 3
2 7

0,0592 [Cr2O72 ][ H ]14

0,0592 3,997.109 (101 )14
lg
1,33
lg
1,14V Hoc:
3 2
6
[Cr ]
6
(16,67.103 )2

[Fe2+] = 6[Cr2O72 ] = 2,398.10 8 M

[ Fe3 ]
50.103

0
,
77

0
,
0592
lg
1,14V
[ Fe 2 ]
2,398.108

0
Edd EFe 3 / Fe 2 EFe
0,0592 lg
3
/ Fe 2

g. Catot: CrO42 + 8 H+ + 6 e Cr + 4 H2O

ne

=>

2000 8 3600
597 mol
96485

350
100 6,76%
1
597 52,00
6

h. Catot: 2 H+ + 2 e H2
2 H2O + 2e H2 + 2 OH

Hoc:

S mol e dng in phn H2CrO4.

n1

350
6 40,4 mol
52,00

=> S mol e dng in phn nc to H2:

n2 597 40,4 556,6 mol

=> VH

556,6
0,08314 298
2
6807 lit 6,807 m3
1,013 Bar

Anot: 2 H2O O2 + 4 H+ + 4 e
597
0,08314 298
VO2 4
3650 lit 3,65 m3
1,013 Bar

1
0,0157 0,232 2 3 626
6
i. %Cu (C18H 33O2 )2
100 23,03% )
9,9
4. Hp cht CrO5
-1

-1

O
+6

Cr
O

H2CrO4 + 2 H2O2

H2SO4

O
O

CrO5 (ete) + 3 H2O

xanh

Cu 4.1. phn tch nh tch crom ngi ta cho dung dch dicromat trong mi trng axit tc dng
vi H2O2 to ra hp cht CrO5 km bn, mu xanh. Hp cht ny c bn ha bng cch chit vo ete
hoc thm phi t mt cng nh pyridin (py) to ra phc thp ng gic CrO5(py).
(a) Hy vit phng trnh phn ng to thnh CrO5.
Trang 32

(b) Hy cho bit s oxi ha ca crom trong CrO5 v trong CrO5(py)? Hy v cu trc khng gian ca
CrO5(py).
Cr2O72 + 4 H2O2 + 2 H+

(a.

H2SO4

2 CrO5 (ete) + 5 H2O

b. +6 v +6;

)
Cu 4.2. (a) D on hin tng, vit phng trnh ion ca cc phn ng xy ra trong cc th nghim
sau:
i/ Thm t K2Cr2O7 ln lt vo mi dung dch: Ba(CH3COO)2; (NH4)2CO3.
ii/ Thm t KNO2 ln lt vo mi dung dch: KMnO4 + H2SO4; KI + H2SO4.
Nu vai tr ca K2Cr2O7 v KNO2 trong cc phn ng trn.
(b) Thm H2O2 vo dung dch K2Cr2O7 + H2SO4 sinh ra sn phm trung gian Cr3(O2)3+ t bn mu xanh
ve d b phn hu cho ion Cr3+. Vit phng trnh ion ca cc phn ng.
(c) Tnh Eo ca cp Cr2O72 /Cr(OH)3.
Cho: EoCr2O72 / 2 Cr3+ = 1,33V; EoMnO4 / Mn2+ = 1,51 V;
EoHNO2/ NO = 1,0 V; EoNO3 / HNO2 = 0,94 V; EoI3 / 3I = 0,55 V.
CH3COOH c pKa = 4,76; H2CO3 c pKa1 = 6,35; pKa2 = 10,33;
H2CrO4 c pKa1 = 0,61, pKa2 = 6,50.
Cr2O72 + H2O

2 HCrO4

K = 10 1,36

Tch s tan ca Cr(OH)3 bng 10 30,8; ca BaCrO4 bng 10 9,9.

Cu 4.3. Cho gin qu trnh kh th kh: qu trnh kh din ra theo chiu mi tn, th kh chun
c ghi trn cc mi tn v o pH = 0.
+0,293
Cr2O72-

+0,55

Cr(V)

+1,34

Cr(IV)

E0x

Cr3+

-0,408

E0y

Cr2+

Cr

-0,744

(a) Tnh E0x v E0y.

(b) Da vo tnh ton, cho bit Cr(IV) c th d phn thnh Cr3+ v Cr(VI) c khng?
(c) Vit qu trnh xy ra vi h oxi ha kh Cr2O72 / Cr3+ v tnh bin thin th ca h nhit
298 K, khi pH tng 1 n v.
(d) Phn ng gia K2Cr2O7 vi H2O2 trong mi trng axit (long) c dng nhn bit crom v sn
phm to thnh c mu xanh. Vit phng trnh ion ca phn ng xy ra v cho bit phn ng ny c thuc
loi phn ng oxi ha kh hay khng? Ghi s oxi ha tng ng trn mi nguyn t.
o
Cho: ECr
O
2

2
7

/ Cr 3

1,33V ; R = 8,3145 J.K .mol ; F = 96485 C.mol .

Trang 33

(a. C:

6 0,293 = 0,55 + 1,34 + E0x + 3 (0,744)

=>

E0x = 2,1 V

C:

3 (0,744) = 0,408 + 2E0y

=>

E0y = 0,912 V;

b.

3 Cr(IV) 2 Cr(III) + Cr(VI)

0
ECr

O 2 / Cr ( IV )

C:

Cch 1: K 10

2( 2,1 0, 945)
0, 0592

0,55 1,34
0,945V
2

1,05 .1039

Cch 2: G0 = nFE0pin = 2 96485 (2,1 0,945) = 222,88 kJ/mol < 0.

Vy Cr(IV) t phn hy d ly to Cr(III) v Cr(VI).
c. Cr2O72 + 14 H+ + 6 e 2 Cr3+ + 7 H2O
0
ECr O 2 / Cr 3 ECr
1,33
O 2 / Cr 3

d. pH = 0:

pH = 1:
0
ECr O 2 / Cr 3 ECr

O 2 / Cr 3
2

0,0592 [Cr2O72 ][ H ]14

0,0592
lg
1,33
lg(101 )14 1,19V
3 2
6
[Cr ]
6

Vy khi pH tng 1 n v th th kh ca h gim 0,14V;

d. Cr2O72 + 4 H2O2 + 2 H+ 2 CrO5 + 5 H2O
Khng
oxi ha

phi

-1

-1

phn

ng

oxi

ha

kh

do

khng

nguyn

no

thay

+6

Cr
O

O
O

0
Cu 4.4. Cp dicromat /crom(III) ( ECr
O
2

2
7

/ Cr 3

1,380V ) thng c s dng trong ha phn tch.

(a) Hy vit bn phn ng oxi ha kh ca cp trn v cho bit dung dch crom(III)/ dicromat
(c(Cr3+)=c(Cr2O72 )= 1 mol/lit) c oxi ha c ioua thnh iot t dung dch trung ha c E(I2/I) = E(I2/I)
= +0,54 V khng.
Mu vng m ca ion cromat v mu da cam m ca ion dicromat thng c s dng pht hin
ra crom. V d crom(III) oxit c un nng chy vi kali nitrat v natri cacbonat, dung dch Cr(III) phn
ng vi hydro peoxit, natri peoxo isunphat, brom l nhng th nghim c dng pht hin Cr(III).
(b) Hy vit phng trnh ca bn phn ng trn. Hy cho bit vai tr ca natri nitrat v natri cacbonat
trong phn ng u tin.
Cn c vo th kh chun ca cp brom/ bromua (E (Br2/Br) = +1,065 V) c th thy phn ng gia
Cr3+ vi brom l khng xy ra iu kin chun.
(c) Hy tnh gi tr pH ti thiu cn thit lp phn ng xy ra. Bit nng ca cc cu t khc u
bng 1 M.

Trang 34

Mt s cu t c mt trong dung dch c th gy cn tr n php phn tch nh tnh Cr(III). V d nu

s dng hidro peoxit th cc ion bromua v ioua s gy cn tr, cn nu s dng brom th Mn2+ s gy cn
tr.
(d) Hy gii thch ti sao cc cu t trn li gy cn tr n php phn tch.
Mt phn ng khc pht hin crom l phn ng ca dicromat vi hidro peoxit. Sn phm to thnh
c mu xanh thm:
Cr2O72 + 4 H2O2 + 2 H+ 2 CrO5 + 5 H2O
(e) Hy cho bit cht oxi ha v cht kh trong phn ng trn.
(a. Cr2O72 + 14 H+ + 6 e 2 Cr3+ + 7 H2O
C: ECr O
2

2
7

=> ECr O
2

2
7

/ Cr

0
ECr

O 2 / Cr 3

/ Cr 3

EI

/I

0,0592 [Cr2O72 ][ H ]14

0,0592
lg
1,38
lg(10 7 )14 0,41V
3 2
6
[Cr ]
6

, tc phn ng oxi ha ioua khng xy ra.

b. Cr2O3 + 3 KNO3 + 2 K2CO3 2 K2CrO4 + 3 KNO2 + 2 CO2

KNO3: cht oxi ha
K2CO3: lm gim nhit nng chy ca hn hp
2 Cr(OH)3 + 3 H2O2 + 4 OH 2 CrO42 + 8 H2O
Hoc:

2 Cr3+ + 3 H2O2 + H2O Cr2O72 + 8 H+

2 Cr3+ + 3 S2O82 + 7 H2O Cr2O72 + 6 SO42 + 14 H+

Hoc: 2 Cr(OH)3 + 3 S2O82 + 10 OH 2 CrO42 + 6 SO42 + 8 H2O

2 Cr(OH)3 + 3 Br2 + 10 OH 2 CrO42 + 6 Br + 8 H2O
Hoc: 2 Cr3+ + 3 Br2 + 7 H2O Cr2O72 + 6 Br + 14 H+
c. phn ng xy ra c th ECr O
2

=> ECr O
2

2
7

/ Cr 3

1,38

2
7

/ Cr 3

EBr

/ Br

0,0592
lg[ H ]14 1,065V
6

=> [H+] < 5,24.10 3 (pH > 2,28)

Vy pH > 2,28 th Br2 oxi ha c Cr3+.
d.

H2O2 + 2 Br Br2 + 2 OH
H2O2 + 2 I I2 + 2 OH

Br2 v I2 sinh ra c mu lm cn tr s quan st mu ca cromat.

5 Br2 + 2 Mn(OH)2 + 12 OH 2 MnO4 + 10 Br + 8 H2O
Mu tm ca pemanganat lm cn tr s quan st mu ca cromat.
e. Khng c cht oxi ha v khng c cht kh do khng c nguyn t no thay i s oxi ha
-1

-1

O
+6

Cr
O

O
O

)
Trang 35

5. ng dng ca crom

Vic a crom vo thp lm tng cao cng, bn nhit, bn n mn v bn ha cht ca cc

loi thp. V d thp khng g (inox) cha 18 25% Cr.
Crom kim loi c s dng rng ri m ln b mt kim loi lm lp bo v chng n mn cho cc
dng c, my mc, thit b, gia dng...
Nhiu hp cht ca crom c s dng lm cht to mu, v d ch cromat PbCrO4 c s dng lm cht
to mu vng cho sn, ch cromat baz (PbCrO4Pb(OH)2) c s dng lm cht to mu . Cr2O3 c s
dng lm cht to mu xanh trong ngnh cng nghip knh v gm. Cr(III) c s dng lm cht to mu
cho ruby nhn to.
Mui cromat c s dng bo qun g khi mi, mt. Mui crom(III) c s dng trong ngy
thuc da. Cromit v crom(III) oxit c s dng lm vt liu chu la. Mt vi hp cht ca crom c s
dng lm cht xc tc. Axit cromic l cht oxi ha mnh thng c s dng lm cht ty ra dng c
thy tinh trong phng th nghim.
Cu 5.1. Qu trnh m crom c thc hin bng cch in phn dung dch axit cromic. Vt cn m
ng vai tr catot v anot l in cc tr. Mt bnh in phn cha 100,0 lit dung dch CrO 3 c nng
0,230 kg/ l.
in phn dung dch vi cng dng 1500 A trong khong thi gian 10,0 gi. Sau qu trnh in
phn khi lng catot tng 0,679 kg.
(a) Hy cho bit hiu sut ca qu trnh in phn iu ch crom.
(b) Hy tnh t l th tch kh thot ra catot v anot ( cng iu kin).
Thc nghim cho thy t l th tch kh thot ra catot v anot ( cng iu kin) l:
VC
1,603
VA

(c) Hy gii thch s khc nhau gia gi tr tnh c (b) v gi tr thc nghim.
(d) Hy tnh th tch kh thc t sinh ra anot v catot ( ktc).
(a. C:

ne

It 1500 10 3600

559,7 mol
F
96485

CrO42 + 8 H+ + 6 e Cr + 4 H2O
S mol electron do cromat nhn l:
ne'

679
6 78,35 mol
52,00

Hiu sut ca qu trnh in phn iu ch crom:

H

ne' 78,35

100 14,0%
ne 559,7

b. Gi thit rng ch c kh hidro thot ra catot v oxi thot ra anot.

Anot (+): 2 H2O O2 + 4 H+ + 4e
Catot (): 2 H+ + 2e H2
C:

nH 2

ne ne' 559,7 78,35

240,7 mol
2
2

Trang 36

nO2

=>

ne 559,7

139,9 mol
4
4

VC nH 2

1,721
VA nO2

c. Thc t c nhng qu trnh ph khc xy ra, v d:

CrO42 + 8 H+ + 3e Cr3+ + 4 H2O
d. CrO42 + 8 H+ + 6 e Cr + 4 H2O
78,35 mol
2 H+ + 2e H2
2x

2 H2O O2 + 4 H+ + 4e
y

4y

C: 78,35 + 2x = 4y
VC nH 2 x

1,603
VA nO2 y

=> x = 158,2;

y = 98,7

=> VH2 = 158,2 22,4 = 3,54.103 lit

VO2 = 98,7 22,4 = 2,21.103 lit)
Cu 5.2. Ch cromat c s dng rng ri lm cht mu, tuy nhin c hai thnh phn c mt trong cht
ny u c c tnh i vi ngi.
(a) Mt mu nc ngm c bo ha PbCrO4 (r) v c pH = 6,00. Hy tnh nng cn bng ca Pb2+,
CrO42, HCrO4 v Cr2O72. Cho cc hng s cn bng:

Ksp [ Pb 2 ][CrO42 ] 2,82.1013

Ka 2

[ H ][CrO42 ]
3,34.10 7

[ HCrO4 ]

[Cr2O72 ]
KD 2
3,13.1014
2 2
[ H ] [CrO4 ]

KW [ H ][OH ] 1,00.1014
(b) Bit trong d dy ca mt ngi b nhim c crom c nng cn bng ca HCrO 4 v Cr2O72
bng nhau. Gi thit dch d dy c pH = 3,0. Hy tnh nng tng cng ca crom ha tan c trong d dy
ca ngi ny.
(a. Cc cn bng xy ra:
PbCrO4 (r)
CrO42 + H+

Pb2+ + CrO42
HCrO4

Ka 2

Ksp [ Pb 2 ][CrO42 ] 2,82.1013

[ H ][CrO42 ]
3,34.10 7
[ HCrO4 ]

(1)
(2)

Trang 37

2 CrO42 + 2 H+

Cr2O72 + H2O

KD

[Cr2O72 ]
3,13.1014 (3)
[ H ]2[CrO42 ]2

C: S = [Pb2+] = [CrO42 ] + [HCrO4 ] + 2 [Cr2O72 ]

(4)

[ H ][CrO42 ] 106 [CrO42 ]

2,994[CrO42 ]
Ka2
3,34.10 7

(2) =>

[ HCrO4 ]

(3) =>

[Cr2O72 ] K D [ H ]2[CrO42 ]2 3,13.1014 (106 )2[CrO42 ]2 313[CrO42 ]2

(4) =>

2,82.1013
[CrO24 - ] 2,994[CrO24- ] 2 313[CrO24- ]2
2[CrO4 ]

=>

626[CrO24- ]3 3,994[CrO24- ]2 2,82.1013 0

=>

[CrO42 ] = 2,66.10 7 M
[ Pb 2 ]

2,82.1013
1,06.10 6 M
-7
2,66.10

[ HCrO4 ] 2,994 2,66.107 7,96.107 M

[Cr2O72 ] 313 (2,66.107 )2 2,21.1011 M

b. C:

[ HCrO4 ]

[ H ][CrO42 ] 103[CrO42 ]

2994[CrO42 ]
Ka2
3,34.10 7

[Cr2O72 ] K D [ H ]2[CrO42 ]2 3,13.1014 (103 )2[CrO42 ]2 3,13.108[CrO42 ]2

=>

2994[CrO42 ] 3,13.108[CrO42 ]2

=>

[CrO42 ] = 9,57.10 6 M
[Cr2O72 ] [ HCrO4 ] 2994 9,57.106 0,02864M

=>

CCr = [CrO42 ] + [HCrO4 ] + 2 [Cr2O72 ]

= 9,57.10 6 + 3 0,02864 = 0,0860 M)

Cu 5.3. Cc hp cht ca crom (VI), c bit l cc hidroxit c tnh oxi ha rt mnh. Trong phng th
nghim ngi ta li dng tnh oxi ha ca crom(VI) loi tr kh hidro sunfua. Trong mt th nghim
ngi ta sc kh CO2 c ln H2S vo dung dch kali dicromat c mt axit sunfuric, cht khng tan mu vng
c to thnh v dung dch chuyn sang mu xanh.
(a) Hy vit cng thc ca cc hidroxit crom(VI) m bn bit.
(b) Hy vit phn ng xy ra trong qu trnh tinh ch kh CO2.
(c) Hy cho bit c th dng phng php trn loi kh SO2 ln trong kh CO2 c khng? Nu
c hy vit phng trnh phn ng xy ra.
(a. H2CrO4; H2Cr2O7; H2Cr3O10; H2Cr4O13;... nCrO3.CrO2(OH)2;
b. 3 H2S + K2Cr2O7 + 4 H2SO4 Cr2(SO4)3 + K2SO4 + 3 S + 7 H2O
c. 3 SO2 + K2Cr2O7 + H2SO4 Cr2(SO4)3 + K2SO4 + H2O
Cu 5.4. (a) Trong mi trng axit, ion cromat mu vng (CrO42 ) chuyn ha thnh ion dicromat mu
da cam (Cr2O72 ). Hy vit phng trnh phn ng.
(b) S oxi ha ca nguyn t kim loi trong ion cromat v ion dicromat bng bao nhiu?
(c) Phn ng vit (a) c phi l phn ng oxi ha kh khng? Gii thch.
Trang 38

(d) Hy cho bit yu t chnh nh hng n v tr ca cn bng trn.

(e) Hy v cu trc hnh hc ca CrO42 v Cr2O72 .
Vt cn m crom c nhng vo dung dch Cr2O72 trong mi trng axit, vt ny ng vai tr l catot
trong bnh in phn. (Cr = 51,996; 1 F = 96485 C)
(f) Bit rng ti anot xy ra qu trnh oxi ha nc, hy vit cc bn phn ng xy ra mi in cc v
phn ng tng cng xy ra trong qu trnh in phn.
(g) C bao nhiu mol kh oxi thot ra khi c 52,0 g crom kt ta ti in cc?
(h) Nu cng dng in l 10,0 A th phi mt bao lu thu c 52,0 g crom?
(i) Xt v mt ha hc th ti sao crom li thng c s dng m trn b mt cc kim loi?
(a. 2 CrO42 + 2 H+

Cr2O72 + H2O

b. +6, +6;
c. khng, khng c nguyn t no thay i s oxi ha.
d. pH;
e.
O
Cr
O

Cr

O
O

Cr

O
O

H2O 1/2 O2 + 2H+ + 2e

f. Anot (+)

Cr2O72 + 14 H+ + 12e 2 Cr + 7 H2O

Catot ()

Cr2O72 + 2 H+ 2 Cr + H2O + 3 O2
1

1,5

g. 1,5 mol;
h. ne It 6
F

=> t 6 F 6 96485 57891 s 16,1 h

I

10

i. Crom phn ng vi oxi to ra lp mng oxit Cr2O3 rt mng, bn v trong sut, gip bo v b mt
kim loi khi b n mn)
Cu 5.5. Cho quy trnh iu ch 4 cht mu v c nh sau:
1) un nng hn hp dng bt mn cha 5,0 g natri dicromat v 0,62 g lu hunh 800C. Ha tan sn
phm vo nc.
2) un nng hn hp dng bt mn cha 3,0 g ch (II) oxit v 1,0 g thic (IV) oxit 650C.
3) un nng ch (II) oxit trong khng kh.
4) un nng hn hp dng bt mn cha 2,0 g silic dioxit, 0,66 g ng (II) oxit, 0,83 g canxi cacbonat
v 0,75 g borat 900C trong vi ngy.
(a) Hy vit cc phng trnh phn ng xy ra.
(b) Hy cho bit vai tr ca borat trong th nghim 4?
Trang 39

(c) Hy nu thm mt cht mu lc (cha st), mt cht mu vng (cha ch), mt cht mu xanh (cha
ng) v mt cht mu (cha thy ngn) v nu phng php iu ch cc cht mu trn.
Trong mt xng v tranh c mt ci can mt nhn cha cht bt mu xanh. xc nh thnh phn
ca cht bt c trong can, ngi ta cn 1,818 g mu, ha tan vo nc v nh mc n vch trong bnh nh
mc 100,00 ml bng axit sunfuric. Ly 10 ml dung dch ri thm vo lng d dung dch KI, chun
hn hp thu c bng dung dch natri thiosunfat 0,100 M thy va ht 16,45 ml.
(d) Hy cho bit kim loi no c phn tch? Hy vit cc phn ng xy ra v tnh thnh phn % theo
khi lng ca kim loi trong mu.
(e) Hy cho bit cht bt mu xanh ny c th l cht mu c iu ch phn (a) khng? Gii thch.
Php phn tch khc s cho bit thnh phn chnh xc ca cht bt mu xanh. Ly 2,000 g mu v un
nng trong iu kin khng c khng kh. Thu c 1,439 g cht rn mu en, hi nc v cht kh lm c
nc vi trong.
(f) Hy xc nh thnh phn ca cht bt mu xanh.
Na2Cr2O7 + S Na2SO4 + Cr2O3

(a.

2 PbO + SnO2 Pb2SnO4

6 PbO + O2 2 Pb3O4
4 SiO2 + CuO + CaCO3 CaCuSi4O10 + CO2
b. Vai tr ca Na2B4O7.10H2O l lm cht chy, lm gim nhit nng chy ca hn hp.
c. Cht mu lc cha st: K[FeIIIFeII(CN)6] hoc Fe4III[FeII(CN)6] 3
FeCl3 + K4[Fe(CN)6] K[FeIIIFeII(CN)6] + 3 KCl
4 FeCl3 + 3 K4[Fe(CN)6] Fe4III[FeII(CN)6] 3 + 12 KCl
Cht mu vng cha ch: PbCrO4.
Pb(NO3)2 + K2CrO4 PbCrO4 + 2 KNO3
Cht mu xanh cha ng: Cu(CH3COO)2 3Cu(OH)2.
CuO + 2 CH3COOH + 4 H2O Cu(CH3COO)2 3Cu(OH)2 2H2O
Cht mu cha thy ngn: HgS (xinabar dng mu )
Hg(NO3)2 + H2S HgS + 2 HNO3
d. ng
2 Cu2+ + 4 I 2 CuI + I2
I2 + 2 S2O32 2 I + S4O62
1
0,1 16,45.103 2 10 63,54
2
%Cu
100 57,5%
1,818

e. %Cu (trong CaCuSi4O10) = 16,9%, khng phi cht mu c iu ch phn (a);

f. CuCO3Cu(OH)2)
Cu 5.6. Nguyn t crom c bn knh l 126 pm v khi lng ring ca crom l 7,14 g/ml. Bit crom
kt tinh dng tinh th lp phng.
Trang 40

(a) Hy xc nh
NA = 6,0221023 mol1.

kiu

tinh

th

ca

crom

da

vo

cc

liu

cho

trn.

Php phn tch nh tnh Cl c tin hnh nh sau: Hn hp khan gm cht cha bit v kali
dicromat c un nng vi dung dch H2SO4 c. Kh thot ra c dn qua dung dch NaOH, nu dung
dch c mu vng chng t c cht cha bit c mt clo.
(b) Hy cho bit hp cht bay hi no ca crom c to thnh trong phn ng trn? Hy v cu
trc ca hp cht ny. Bit rng s oxi ha ca Cr v Cl khng thay i trong phn ng.
Axit ha dung dch kali cromat cho ion dicromat mu da cam, tip l to thnh cc ion tri v
tetracromat mu m. Nu s dng dung dch axit sunfuric c s thu c kt ta mu khng cha
kali.
(c) Hy vit cc phn ng xy ra v v cu trc ca cc ion. Hy cho bit cu trc ca cht kt
ta mu .
Gin Latimer ca crom trong mi trng axit (pH=0) v trong mi trng kim (pH=14) nh sau:

(d) Hy xc nh cc gi tr th kh cn thiu.
(e) Hy cho bit Cr(V) v Cr(IV) c t phn hy d ly khng? Hy cho bit hng s cn bng ca phn
ng phn hy d ly Cr2+.
(f) Hy tnh tch s tan ca crom (III) hidroxit v hng s bn tng cng ca anion phc
tetrahidroxo cromat (III).
Gin Latimer ca oxi trong mi trng axit (pH=0) v mi trng kim (pH=14) nh sau:

Trang 41

(g) Hy cho bit c phn ng no xy ra khi pH ca dung dch cha cromat, Cr(III) v hidro
peoxit c gi tr bng 0 v bng 14? Tnh sut in ng chun ca cc phn ng .
(a. TH1: mng lp phng n gin:
a 2R 2 126 252 pm 2,52.10 8 cm

52,0
5,40 gam / cm3
6,022.10 (2,52.108 )3

=>

d 1

=>

khng hp l

23

TH2: mng lp phng tm mt:

a

4 R 4 126

356,4 pm 3,564.108 cm
2
2
52,0
7,63gam / cm3
6,022.10 (3,564.108 )3

=>

d 4

=>

khng hp l

23

TH3: mng lp phng tm khi:

a

4 R 4 126

291 pm 2,91.108 cm
3
3

=>

d 2

=>

hp l;

52,0
7,01gam / cm3
6,022.10 (2,91.108 )3
23

Vy crom kt tinh theo kiu lp phng tm khi.

b. CrO2Cl2, cromyl clorua;

c.

2 CrO42 + 2 H+ Cr2O72 + H2O

3 CrO42 + 4 H+ Cr3O102 + 2 H2O
4 CrO42 + 6 H+ Cr4O132 + 3 H2O
CrO42 + 2 H+ CrO3 + H2O

Cu trc ca cc ion:

Trang 42

d. Cr2+ Cr

Eo = 0,9V;

Cr(V) Cr(IV)

Eo = 1,35V;

Cr2O72 Cr(III)

Eo = 1,33V;

e.

iu kin: E2 > E1.

C Cr(V) v Cr(IV) u t phn hy d ly.
3 Cr2+
f.

2 Cr3+ + Cr

6,08.1017

Cr + 3 OH Eo = 1,33V

Cr(OH)3 + 3e
Cr3+ + 3e

K 10

2 ( 0, 9 0, 42)
0, 0592

Eo = 0,74V

Cr

Cr(OH)3

Cr3+ + 3 OH

Cr(OH)4 + 3e

Cr + 4 OH

Cr3+ + 3e

T = 1,26.10 30
Eo = 1,33V
Eo = 0,74V

Cr

Cr3+ + 4 OH

Cr(OH)4

= 7,92.10 29

g. pH = 0:
Cr2O72 + 3 H2O2 + 8 H+ 2 Cr3+ + 3 O2 + 7 H2O
Eo =1,33 0,695 = 0,635 V
pH = 14:
2 Cr(OH)4 + 3 HO2 2 CrO42 + 5 H2O + OH
Eo = 0,87 (0,72) = 1,59 V)
Cu 5.7. Ngi ta tin hnh tch ion bari v srontri ra khi nhau da vo tan khc nhau ca mui
cromat. Nng cromat trong dung dch c th iu chnh bng cch thay i pH.
2 H+ + 2 CrO42

Cr2O72 + H2O

K = 1,50 1015

Cho cc gi tr tch s tan: TBaCrO4 = 8,5 10 11; TSrCrO4 = 3,6 10 5.

(a) Hy tnh tan ca BaCrO4 v SrCrO4 trong mi trng baz mnh.
Trang 43

(b) pH ca dung dch K2Cr2O7 0,10 mol/lit c iu chnh n 3,00 bng cch s dng m axetat.
Hy tnh nng Cr2O72 v CrO42 trong dung dch thu c.
Thm vo hy tnh gi tr nng nh nht ca Ba2+ v Sr2+ trong dung dch ny kt ta cromat
tng ng bt u xut hin.
(c) iu ch dung dch m ngi ta s dng dung dch axit axetic
0,10 mol/lit. Hy tnh khi lng natri axetat cn thm vo 1 lt dung dch trn thu c dung dch m c
pH
=
3,00.
Bit
hng
s
phn
li
ca
axit
axetic
5
Ka = 1,78 10 .
Di y l gin Latimer ca crom trong mi trng axit (pH = 0).
+0,293
Cr2O72- +0,55
da cam

Cr(V)

+1,34

Cr(IV)
xanh

[Cr(H2O)6]3+
tm

-0,408

[Cr(H2O)6]2+
lc
-0,744

Cr

(d) Hy xc nh cc gi tr th x v y.
(e) Hy cho bit Cr(IV) c b phn hy d ly to ra Cr(III) v Cr(VI) khng? Gii thch.
(f) Hy vit bn phn ng kh ca cp Cr2O72 /Cr3+. Hy tnh s gim th kh ca cp oxi ha kh
ny khi pH tng thm 1 n v.
Xt phc mu tm [CrCl2(ox)2]3 .
(g) Hy cho bit s phi tr ca phc trn.
(h) Hy cho bit hnh hc phn t ca phc.
(i) Hy gi tn ca ion phc.
(k) Hy vit cc ng phn lp th ca phc trn.
(a. Trong mi trng kim th CrO42 b thy phn khng ng k:
Ba2+ + CrO42

BaCrO4

=>

S TBaCrO4 8,5.10 11 9,22.10 6 M

=>

S ' TSrCrO4 3,6.105 6.103 M

b. 2 H+ + 2 CrO42

Cr2O72 + H2O

K = 1,50 1015

[Cr2O72 ] + 0,5 [CrO42 ]= 0,1

C:
K

[Cr2O72 ]
1,50.1015
[ H ]2 [CrO42 ]2

[Cr2O72 ] = 0,1 M

=>

[CrO42 ] = 8,16.10 6 M
kt ta BaCrO4 bt u xut hin:
[ Ba 2 ]

TBaCrO4
[CrO42 ]

8,5.1011
1,04.105 M
8,16.10 6

Trang 44

 kt ta SrCrO4 bt u xut hin:

[ Ba 2 ]

TBaCrO4
[CrO42 ]

3,6.105
4,41 M
8,16.10 6

c. [ H ] K a C A [ H ] [OH ]
C B [ H ] [OH ]

C:

[OH ] << [H+] << CA

=>

[ H ] Ka

hay

103 1,78.105

=>

CB = 7,8.10 4 M

=>

mCH3COONa = 7,8.10 482 = 0,064 gam

d.

x = 2,1 V

CA
CB [ H ]
0,1
CB 103

y = 0,912V
e. C:

0
ECr
0,945V
O 2 / Cr ( IV )
2

0
0
ECr
ECr
( IV ) / Cr ( III )
O 2 / Cr ( IV )

=>

=> phn ng phn hy d li t xy ra.

Cr2O72 + 6e + 14 H+ + 5 H2O 2 Cr(H2O)63+

f.

0
ECr
1,33V
O 2 / Cr 3
2

C:

0
ECr O 2 / Cr 3 ECr

O 2 / Cr 3
2

0,0592 [Cr2O72 ][ H ]14

lg
6
[Cr 3 ]

Xt: [Cr2O72 ] = [Cr3+] = 1M; [H+] = 0,1 M

ECr O 2 / Cr 3 1,33

=>

0,0592
lg 0,114 1,19V
6

Epin = 1,19 1,33 = 0,14 V

=>

Vy khi pH tng thm 1 n v th th ca cp gim 0,14V;

g. 6;
h. bt din;
i. icloro bisoxalato cromat(III)
k.
3-

Cl
O

O
Cr

Cl
O

3-

Cl

Cr
O

Cl

Cr
O

3-

Cl

Cl
O

Trang 45