Hoa vo c

PHAN

NG
OXY HOA KH

PHN NG OXY HA KH
I.

MT S KHI NIM V PHN NG OXY HA

KH

II.

CC YU T NH HNG N TNH OXY HA,

KH CA CC CHT

III.

NH GI KH NNG THAM GIA PHN NG O

XY HA KH CA CC CHT

IV.

S N NH CA CC CHT OXY HA V KH
TRONG MI TRNG NC

I. MT S KHI NIM C BN
1.

nh ngha phn ng oxy ha kh

2.

Cp oxi ha - kh lin hp
a.

nh ngha

b.

S tng ng gia phn ng oxy ha - kh v phn ng ax

it baz

3.

Cn bng phn ng oxy ha kh

4.

P.ng OXH K v qu trnh in cc

a.

Phn ng in ha

b.

Phn ng in cc v phng trnh Nernts

PHAN NG OXY
HOA - KH

nh ngha: Phan ng oxy hoa kh la phan ng trong o co

s chuyen van electron t chat
kh sang chat oxy hoa dan en
lam thay oi so oxy hoa cua
cac nguyen to ong vai tro
chat oxy hoa va chat kh.

a. nh ngha

Cht oxy ha - nhn e. Cht kh - cho e

+ne
aOXH1 + bKh2 cKh1 + dOXH2 (1)
Qu trnh kh:

-ne
aOXH1 + ne cKh1

Qu trnh oxy ha:

bKh2 ne dOXH2

Cc cht oxy ha v kh trong mi bn phn ng

to thnh mt cp OXH - K lin hp.
Phn ng (1) c hng s cn bng:
K cb

[ Kh1 ]c [OXH 2 ] d

[OXH 1 ] a [ Kh2 ]b

b. S tng ng gia phn ng oxy

ha - kh v phn ng axit baz

Phn ng axit baz:

- nH+
aAx1 + bBaz2 cBaz1 + dAx2

Ka , K b

+ nH+
Phn ng oxy ha - kh:
+ne
0
OXH / Kh
aOXH1 + bKh2 cKh1 + dOXH2
-ne

a. Phn ng in ha

P OXH K: Cht kh - e trc tip cho cht OXH.

P in ha: cc cht OXH v kh trao i electron
vi cc in cc tng ng.
1 p OXH K 1 qu trnh in cc
P OXH K thun qt trong ngt Ganv:
qu trnh t din ra,
ha nng in nng.
E = + - -.

P OXH K nghch qt trong bnh in phn:

qt cng bc
in nng ha nng.
Engoai > - EGanv.

b. Phn ng in cc v pt Nernst

Phng trnh Nernst:

RT OXH

ln
nF
Kh
0

0.059 OXH

lg
n
Kh
0

Quy c v du ca (theo chu M): ni ln KN

xy ra ca qt in cc. G = - nFE

Phn ng c xt l phn ng kh.

Nu qt kh xy ra trn in cc: > 0.

Nu qt kh khng xy ra trn in cc): < 0.

V d:

Zn2+ + 2e Zn

0 = -0.763V

Cu2+ + 2e Cu 0 = +0.337V

: tnh OXH ; tnh kh

Trong mot phan ng oxy hoa- kh

luon co hai qua trnh:
Qua trnh nhan electron qua trnh kh
Ox1 + e Kh1 ( S +2e S2-)
Chat nhan electron la chat oxy hoa
Qua trnh nhng electron qua trnh oxy hoa
Kh2 e Ox2 ( Fe 2e Fe2+)
Chat nhng electron la chat kh
Ket hp hai qua trnh c phan ng oxy
hoa - kh:
Ox1 + Kh2 = Ox2 + Kh1 ( S + Fe FeS )

Cap oxy hoa kh lien hp

S/S2-va Fe2+/Fe trong th du tren la cac cap oxy hoa kh lien hp

Nhac lai: Can bang

phan ng O K

Nguyen tac 1:

Tong so electron cho cua chat kh phai

bang tong so electron chat oxy hoa
nhan vao.

Cac bc tien hanh can bang.

Bc 1: Xac nh s thay oi so oxy

hoa cua cac chat.
Bc 2: Lap phng trnh electron ion,
vi he so sao cho ung qui tac tren.
Bc 3: Thiet lap phng trnh ion cua
phan ng.
Bc 4: Can bang theo he so t lng.

Cn bng phn ng OXH K (b qua)

Mi trng

Ly [O] t MT

y [O] ra MT

Axit (H+, H2O)

H2O [O] + 2H+

[O] + 2H+ H2O

Trung tnh(H2O)

H2O [O] + 2H+

[O] + H2O 2OH-

Baz (OH-, H2O)

2OH- [O] + H2O

[O] + H2O 2OH-

V du:
Al + CuSO4 Al2(SO4)3 + Cu
Al -3e Al+3

2
Cu+2 + 2e Cu X3
_______________________
X

2Al + 3Cu+2 = 2Al+3 + 3Cu

2Al + 3CuSO4 2Al2(SO4)3 +

3Cu

Nguyen tac 2:

oi vi phan ng O K xay ra trong

moi trng acid neu dang Ox cua chat
Ox co cha nhieu nguyen t Oxy hn
dang kh cua no th phai them H+ vao
ve trai (dang Ox) va them nc vao
ve phai (dang kh).
Neu dang kh cua chat Kh cha t
nguyen t Oxy hn dang Ox cua no th
them nc vao ve trai (dang Kh) va
H+ vao ve phai (dang Ox).

Thieu O ben nao, them H2O ben o,

ben kia them H+

V du:

KMnO4 KNO2 H 2 SO4 MnSO4 KNO3 K 2 SO4 H 2O

MnO4 5e Mn2
NO2 2e NO3
MnO4 5e 8 H Mn 2 4 H 2O

NO2 2e H 2O NO3 2 H

2
X5
X

2MnO4 5NO2 6H 2Mn 5NO3 3H 2 O

2KMnO4 5KNO 2 3H 2 SO4 2MnSO4 5KNO 3 K 2 SO4 3H 2 O

Nguyen tac 3:

Phan ng O K xay ra trong moi

trng base, neu dang Ox cua chat
Ox cha nhieu Oxy hn dang kh th
phai them nc vao ve trai, OH vao ve phai.
Neu dang Kh cua chat Kh cha t Oxy
hn dang Ox cua no th phai them
OH- vao ve trai, nc vao ve phai.

Thieu O ben nao them OH - ben o,

ben kia la H2O.

V du:

KClO 3 CrCl3 KOH K 2 CrO4 KCl H 2 O

ClO3 6e 3H 2 O Cl 6OH

Cr3 3e 8OH CrO42 4H 2 O

2
4

ClO 2Cr 10OH Cl 2CrO 5 H 2O

KClO 3 2CrCl3 10KOH 7KCl 2K 2 CrO4 5H 2 O

Nguyen tac 4:

Phan ng O-K trong moi trng

trung tnh. Neu dang Ox cua chat Ox
cha nhieu nguyen t Oxy hn dang
Kh cua no th phai them nc vao
ve trai, OH- vao ve phai.
Neu dang Kh cua chat Kh cha t
nguyen t Oxy hn dang Ox cua no
th phai them nc vao ve trai, H +
vao ve phai.

Them nc ve trai het, ve phai:

OH- neu them e, H+ neu mat e.

V du:

KMnO4 KNO 2 H 2 O MnO2 KNO 3 KOH

MnO 3e 2H 2 O MnO2 4OH

NO 2e H 2 O NO 2H

2
X

3 6H
2 MnO4 3NO2 7 H 2O 2MnO2 3 NO3 8OH

2MnO 3NO H 2 O 2MnO2 3NO 2OH

2KMnO4 3KNO 2 H 2 O 2MnO2 3KNO 3 2KOH

III. nh gi kh nng tham gia phn

ng oxy ha kh ca cc cht
1.

S dng cc hm nhit ng ha hc

2.

Th kh v phng trnh Nernst

3.

Gin Latimer

4.

Gin Frost

II. CAC YEU TO ANH HNG

EN TNH OXY HOA - KH
CUA CAC CHAT

Kha nang oxy hoa kh cua chat

phu thuoc cac yeu to sau:
1- ac iem cau tao lp vo electron
va trang thai oxy hoa cua nguyen t
. The hien qua cau tao bang he
thong tuan hoan
2- o ben vng cua chat.
3- Moi trng tien hanh phan ng.

Mt s quy tc xc nh s
oxi ha bn ca nguyn t
a.

S oxi ho khng

b.

Cc nguyn t h s

c.

Cc nguyn t h p

d.

Cc nguyn t h d

e.

Cc nguyn t h f

f.

Quy tc chung

a. S oxi ha khng

Kim loi mnh v phi kim mnh c mc oxi ha

khng km bn

Kim loi cng yu, phi kim cng yu: mc oxi ha

khng cng bn.

Cc nguyn t lng tnh u c mc oxi ha

khng bn

b. Cc nguyn t h s

Cc nguyn t h s ch c mt s oxi ha dng

bn vng trng vi s th t ca phn nhm.

V du: Na(IA) co so oxy hoa ben +1;

Ca(IIA) co so oxy hoa ben +2

Ring H c hai s oxi ha +1 v -1 nhng s oxi

ha +1 l bn vng hn hn s oxi ha -1.

c. Cc nguyn t h p

Quy tc chn l ca Mendeleev.

Cc mc oxi ha c cu hnh bo ha mt lp
(ns2np6) hoc mt phn lp (ns2) bn hn hn.

Trong mt chu k t tri qua phi s oxi ha

dng cao nht ca cc nguyn t km bn dn
(v rat de lay lai e a mat do mat
o ien tch dng tang dan va r
giam dan).

nh lut tun hon th cp.

Qui tac chan le

Mendeleev.
Nguyen
to phan nhom

chan co cac
so oxy hoa chan ben hn han cac so
oxy hoa le.
Nguyen to phan nhom le co cac so
oxy hoa le ben hn han cac so oxy
hoa chan.

V du: Cl (VIIA) co cac so oxy hoa -1, +1,

+3, +5, +7 ben hn cac so oxy hoa chan.
S (VIA) co cac so oxy hoa -2, +2, +4, +6
ben hn cac so oxy hoa le.
Xe (VIIIA) hien ch biet cac hp chat co
so oxy hoa +2, +4, +6 va +8.

V du:
Cl co cac mc oxy hoa ben hn: -1
(cau hnh Ar) va +7 (Ne), va +5 v s
dung het 5 e phan lp 3p.
S co cac mc oxy hoa ben hn: -2
(cau hnh Ar), +6 (Ne) va +4 v s dung
het 4 e phan lp 3p.

V du: Xet day chu ky III (Al, Si, P, S va

Cl)

Al: Mc oxy hoa + 3 rat ben vng,

nhom trong cac hp chat ieu kien
thng eu co so oxy hoa +3.

Si: Mc oxy hoa +4 rat ben vng (nh

Al).

P: ion PO43- kha ben, nhng khong co tnh

2
oxy hoa duHPO
trong
moi trng acid am
4
ac.

PO 34

H3PO4 + 2H++2e = H3PO3 + H2O, o = -0.276V,

pH = 0
+ 2H2O + 2e =

+ 3OH-, o = -1.12V, pH = 14

S: ion SO42- khong co tnh oxy hoa trong moi

trng kiem, co tnh oxy hoa rat yeu
moi trng acid (pH = 0) va la chat oxy hoa
kha manh khi la acid sulfuric nguyen chat
(oxy hoa c bac).
SO42- + 4H+ + 2e = H2SO3 + H2O, o = 0.17V, pH = 0

SO42- + H2O + 2e = SO32- + 2OH-, o = -0.93V,pH

=14
Cl: Hp chat +7 cua Cl la chat oxy hoa
manh. ClO4-la chat oxy hoa manh pH = 0,
HClO4 no khi tiep xuc cac chat hu c
hoac khi b chieu sang. Tnh oxy hoa yeu
trong moi trng kiem.
ClO4- + 2H+ + 2e = ClO3- + H2O, o = 1.19V, pH = 0
ClO4- + H2O + 2e = ClO3- + 2OH-, o = 0.36V, pH =14

d. Cc nguyn t h d

Trong mt chu k t tri qua phi cc mc

oxi ha dng cao nht km bn vng dn.

i vi cc ngt d sm, tt c cc e u c th
tham gia to lin kt
i vi cc ngt d mun, ch mt s e (n - 1)d
tham gia to lin kt
Trong hp chat, nguyen t cua
nguyen to d co the cha electron
(n-1)d oc than.

Trong mt phn nhm t trn xung cc

mc oxi ha dng cao nht bn vng dn.

e. Cc nguyn t h f
Mc

oxi ha bn nht ca cc
nguyn t h f l +2

nh luat tuan hoan th

Trong
mot phan nhom chnh: so oxy hoa
cap.
dng cao nhat cua chu ky IV kem ben
ro ret so vi so oxy hoa dng cao nhat
cua nguyen to chu ky III; so oxy hoa
dng cao nhat cua chu ky VI kem ben
ro ret so vi so oxy hoa dng cao nhat
cua nguyen to chu ky V.

V du 1: Xet phan nhom VIIA.

Xet trong cung ieu kien ion BrO 4- oxy hoa
manh hn han ion ClO4-:
ClO4- + 2H+ + 2e = ClO3- + H2O, o = 1.19V, pH = 0
BrO4- + 2H+ + 2e = BrO3- + H2O, o = 1.763V,pH =
0

Hp chat cha At so oxy hoa +7 khong

ton tai trong dung dch nc v no la chat
oxy hoa qua manh, oxy hoa nc giai
phong kh oxy, trong khi o hp chat cua I +7
ton tai trong dung dch.
H5IO6 + H++2e= IO3- +3H2O, o = 1.64V, pH = 0

V du 2: Xet phan nhom IVA.

Hp chat cha Si+4 rat ben, khong co tnh
oxy hoa ngay trong moi trng acid rat
manh, no hau nh khong b kh trong dung
dch nc.
Ge+4 cung khong co tnh oxy hoa trong moi
trng acid (pH=0) nhng rat de b kh ve
so oxy hoa +2.
GeO2 (r) +2H++2e= GeO(r) +H2O, o=-0.12V,pH=0

SnO2 khong the hien tnh oxy hoa pH=0

trong khi o PbO2 la chat oxy hoa rat manh
trong cung ieu kien.
SnO2 (r) +2H++2e= SnO(r) +H2O, o=-0.088V,pH=0
PbO2 (r) +4H++2e= Pb2+ +2H2O, o= 1.445V,pH=0.

V du 3: xet the kh cac hp chat (V)

phan nhom VA
H3PO4 + 2H+ + 2e = H3PO3 + H2O
0,276
H3AsO4 + 2H+ + 2e = HAsO2 + 2H2O
Sb2O5 (r) + 6H+ + 2e = 2SbO+ + 3H2O
NaBiO3 (r) + 4H+ + 2e = BiO+ + Na+ + 2H2O

+0,56
+0,58
> +1,8

Quy luat tuan hoan th cap do viec

xuat hien lan au tien cac phan lp (n-1)d
( chu ky IV) va (n-2)f ( chu ky VI) lam cap
electron ns kem hoat ong hn dan en tang
ot ngot s kem ben vng cua mc oxy
hoa dng cao nhat cua cac nguyen to
thuoc cac chu ky nay so vi cac nguyen to
thuoc chu ky trc o.

Giai thch:

Trong mot phan nhom phu t tren

xuong di mc oxy hoa cao nhat
ben dan.

V du: trong moi trng acid phan

nhom VIB:
0
Ban phan ng kh

(V)

Cr2O72- + 14H+ + 4e 2Cr4+ +

7H2O

+0,95

MoO42- + 4H+ + 2e MoO2 +

2H2O

+0,606

V du 2: Xet phan nhom IVB, da vao the

oxy hoa kh, thay ro Hf(+4) va Zr(+4) ben
hn ro ret so vi Ti(+4).

TiO2++ 2H++e = Ti3+ +H2O,

o=0.1V,pH=0

ZrO2++ 2H++4e = Zr +H2O,

o=-1.5V,pH=0

HfO2++ 2H++4e = Hf +H2O,

o=-1.7V,pH=0
V du 3: Xet phan nhom VIB, da vao the
oxy hoa kh, thay ro Mo(+6) va W(+6) ben
ro ret hn so vi Cr(+6).
Cr2O72-+ 14H++6e = 2Cr3+ +7H2O, o=1.33V,pH=0
MoO22++e = MoO2+

o=+0.48V

WO3(r)+ 2H++2e = W2O5(r) +H2O, o=-0.03V,pH=0

V du1: So oxy hoa cao nhat hien biet en

cua cac nguyen to d chu ky 4:

IIIB

IVB

VB

VIB

VIIB

Sc

Ti

Cr

Mn

Fe

Co

+3

+4

+5

+6

+7

+6

+5

VIIIB

IB

IIB

Ni

Cu

Zn

+5

+5

+2

V du 2:
Cau hnh electron cua ion Cr3+ trong Cr2O3 la
(n-1)d3

Trong mot chu ky t trai qua phai cac

mc oxy hoa dng cao kem ben vng
dan.

V du 1: Xet chu ky III: Ti(4), V(5), Cr(6), Mn(7),

Fe(8), Co(9), Ni(10), Cu(11) (trong ngoac la
tong so e tren 3d4s).
TiO2+ + 2H+ + e = Ti3+ + H2O,
o = 0.1V, pH = 0
VO43- + 6H+ + 2e = VO+ +3H2O,
o = 1.26V, pH =
0
Cr2O72- + 14H+ + 6e = 2Cr3+ +7H2O, o = 1.33V, pH =
0
MnO4- + 8H+ + 5e = Mn2+ + 4H2O, o = 1.51V, pH =
0

Cha tm thay hp chat Fe+8.

FeO42- + 8H++3e = Fe3+ + 4H2O,
o > 1.9V,
pH = 0
Cha tm thay hp chat Co+9, hien ch
biet en cac hp chat Co en +6. Ch
co cac hp chat Co+3 ton tai trong dung
dch nc va chung cung oxy hoa c
nc. Co3+ + e = Co2+, o = 1.84V, pH = 0.
Ni tng t Co, ion Ni3+ khong the ton tai
t do trong dung dch nc, v vay hp
chat ben cua Ni luon mc +2.
Cu cung tng t Ni va Co, trong ieu
kien thng ch biet en Cu (+1,+2).

Quy tac chung

Cac nguyen to mc oxy hoa trung gian

co the ong vai tro chat oxy hoa khi tac
dung vi chat kh hay ong vai tro chat
kh khi tac dung vi chat oxy hoa. Tuy
nhien tnh chat ac trng cua nguyen to
o phu thuoc vao o ben vng cua cac
mc oxy hoa ac trng lan can vi no.
VD: Xet Cl(+5), co tnh oxy hoa v ca Cl(+7)
va Cl(0) eu co tnh oxy hoa.
Xet cac hp chat S(+4): V S(+6) kha ben
vng va hau nh khong the hien tnh oxy
hoa, nen S+4 co tnh kh. Mat khac S+4 co
tnh oxy hoa yeu v S(0) co tnh kh yeu.

Quy tac so sanh e tm tnh oxy hoa kh

ac trng
Nguyen t mc oxy hoa kem ben co xu hng
chuyen ve mc oxy hoa ben. Neu mc oxy hoa
ben cao hn mc oxy hoa kem ben th chat co tnh
kh ac trng. Neu mc oxy hoa ben thap hn
mc oxy hoa kem ben th chat co tnh oxy hoa
ac trng. Neu mc oxy hoa kem ben cua
nguyen t nam gia hai mc oxy hoa ben hn th
chat co ca tnh oxy hoa va tnh kh la ac trng.
V du : H2S co tnh kh ac trng v mc oxy hoa 0
cua S kha ben hn mc oxy hoa 2.
HClO la chat oxy hoa ac trng v mc oxy hoa
ben cua Cl la 1.
Na2SO3 co tnh kh va tnh oxy hoa ac trng v
mc oxy hoa +6 va 0 cua S ac trng hn mc oxy
hoa +4.

2. o ben vng cua

chat
+Nang
lng lien ket trong phan t cang
cao th kha nang hoat ong hoa hoc
cang thap.

V du 1: Oxy co o am ien 3,44 con Clor

co o am ien 3,16 nhng ieu kien
thng, kh Clor la mot chat oxy hoa rat
manh liet con oxy la chat oxy hoa em
du. Nguyen nhan la do O2 co nang
lng lien ket (493 kJ/mol) ln hn han
nang lng lien ket trong phan t Cl2
(239 kJ/mol).

+Ion nam trong hp chat trang thai

ran hoat ong hoa hoc kem han khi
nam trong trang thai t do:

V du: The kh cua ion Pb4+(aq) ln hn

han PbO2

PbO2(r) + 2H+(aq) + 2e- = Pb2+(aq) + 2H2O

o
=+1,449V
Pb4+(aq) + 2e- = Pb2+(aq)
o = +1,694V

Tom lai, hp chat cang ben vng th

kha nang hoat ong hoa hoc cang
kem.

3. nh hng ca mi trng phn ng

oi vi rat nhieu phan ng, moi trng

acid lam tang manh tnh oxy hoa cua chat
oxy hoa va moi trng base lam tang
manh tnh kh cua chat kh.
Trong trng hp nay, khai niem acid base hieu
theo ngha tong quat nhat.
a) Anh hng cua Acid base Bronsted
Lawry en tnh oxy hoa kh:
V du 1: The kh cua ion SO42- tang nhanh khi
chuyen t moi trng base sang moi trng acid:
pH = 0 : SO42- + 2H+ + 2e- = H2SO3 + H2O o = +0,17V

pH = 14: SO42-+H2O + 2e- = SO32- + H2O o = -0,93V

b) Anh hng cua acid base Lewis:

V du: Ion Ag+.aq la mot chat oxy hoa trung bnh
yeu trong dung dch nc:
Ag+ + e- = Ag o = +0,799V
Tuy nhien khi co mat base Lewis CN - th no lai
the hien tnh kh yeu:
Ag(CN)2- + e- = Ag + 2CNo = -0,29V
c) Anh hng cua acid base Usanovich.
Khi hoan nguyen phospho t quang phosphorit
15000C, trong thanh phan phoi lieu co cat. Cat
ong vai tro acid Usanovic lam tang tnh oxy hoa
cua P(V):
2Ca3(PO4)2 + 10C + 6SiO2 = 6CaSiO3 + 10CO + P4
Trong phan ng nay SiO2 tac dung vi photphorit
tao calcisilicat, giai phong phospho oxide.
(Xem file Kh quang phosphorit)

Trong moi trng co mat ion tao hp

chat ion t tan cung lam thay oi tnh oxy
hoa kh cua chat:

V du: Tnh oxy hoa cua ion Cu 2+ tang len ro

ret khi co mat ion Cl- do CuCl la chat t tan
(TCuCl = 1,2.10-6)

Cu2+ + e- = Cu+
o = +0,153V
Cu2+ + Cl- + e- = CuCl(r) o = +0,538V
(trong trng hp nng o ion cloride cao th ng
(I) cloride tan ra v to thanh phc [CuCl2]- co Kkb =
10-5,35
Cu2+ + 2Cl- + e- = [CuCl2]o =
+0,4633V)

1. S DNG CC HM NHIT NG
HA HC

Can c vao ai lng bien thien the ang

ap tieu chuan cua phan ng, chung ta co
the anh gia ve kha nang xay ra phan ng
ve phng dien nhiet ong. oi vi phan ng
nhiet o phong, co the can c vao gia
tr nhiet phan ng, con phan ng nhiet
o cao can c vao ai lng bien thien
entropy phan ng. Cach xem xet tng t nh
oi vi phan ng khong thay oi so oxy hoa.
Can nhan manh rang a so phan ng d pha
cua vo c eu co c che phc tap, do o
luon can khao sat ong hoc khi ng dung
cac phan ng nay.

2. TH KH V PHNG TRNH
Nernst

The kh cho biet o manh cua chat oxy

hoa va chat kh lien hp vi no. The
kh cang ln, chat oxy hoa cang manh va
chat kh lien hp cang yeu va ngc lai.

V du: The oxy hoa kh cua cap Au 3+/Au

trong moi trng acid = +1,68V cho biet Au 3+
la chat oxy hoa rat manh , ngc lai Au la
chat kh het sc yeu (Vang la kim loai
rat ben vng).

3. GIAN O LATIMER

Lewis H. Latimer

The Oxy hoa-Kh cua

cac ban phan ng
rieng le ch thuan
tien khi thanh lap pin
hay trong cac qua trnh
phan tch. Nhng e
khao sat mot qua
trnh chuyen hoa oxy
hoa-kh phc tap th
lai kho khan. Trong
trng
hp
nay
Latimer a ra gian o
mang ten ong e
bieu dien cac qua
trnh phc tap o.

Thiet lap gian o

Latimer

Da tren cac ket qua: G = -nFE, va

trong chuoi phan ng GT = Gi.

V du: Xet trng hp cua Fe.

Ban phan ng E0
= -nFE0
Fe2+ +2e Fe
-0.44V -2F 0.44
Fe3+ +e Fe2+
0.771V -1F0.771
Fe3+ +3e Fe
T o ta co E0T

E0T 0.331V -3FE0T

0
0
n
E

n
E
0
1 1
2 2
E

3
= -0.036V
n
3

V du thiet lap gian o Latimer cho

Iode

IO IO HOI I 2 I
1.589

1.154

1.430

.535

(+7)(+5)(+1)(0)(1)
1.299

2H IO 2e IO H 2 O

5H IO3 4e HOI 2H 2 O

7H IO 4 6e HOI 3H 2 O
4

o
1

G o2
G 3o

2 1.589 4 1.154
1.299
G G G
6
o
o
o
2E1o 4E o2
o
n1FE1 n 2 FE 2 n 3 FE 3
E3
6
o
1

o
2

o
3

Bieu dien gian o Latimer

Cac dang hp chat cua nguyen to c

sap xep theo chieu giam dan so oxy
hoa.
Noi gia cac dang nay la mui ten
kem theo gia tr the oxy hoa-kh cua
qua trnh tng ng.
Tren nguyen tac, the O-K phai giam t
trai sang phai.
Neu nguyen tac nay b vi pham (dang
sau co the ln hn dang trc), th dang
sau o se khong ben vng, rat de b
d ly, tao 2 dang lan can cua no.

V du 1: Gian o Latimer cua Fe bieu

dien nh sau.

V du 2: Gian oD
Latimer cua Mn trong
moi trng acidlyva base.

Cac yeu to anh hng en the O-K,

day Latimer
Tong quat, cac yeu to lam thay oi G
(G =
-nFE) eu anh hng en the O0 hay 0). hay
K (E
cu the
RT aOx
0
0.059 [Ox]

ln
vi
dung 00
lg
nF aKh dch nc
n
[ Kh]

250C th

Cac yeu to nay la:

1/
2/
3/
4/

Nong o.
Nhiet o.
Cac tac chat khac (khong phai kh tr).
pH (trng hp rieng cua trng hp 3).

V du: Khao sat yeu to pH. Vi ClO 4-, trong

moi trng acid va base ta co the O-K nh
sau:
ClO4- + 2H+ + 2e = ClO3- + H2O, o=1.19V,pH=0
ClO4- + H2O + 2e = ClO3- + 2OH-, o=0.36V,pH=14
Trong moi trng acid, v co H + tham gia vao
qua trnh:
0.059 [ClO4 ][ H ]2

1.19

lg

[ClO ]

(V )

V vay tang H+ (gim pH) se dan en tang

, hay tang tnh Oxy hoa, ngc lai.
Tng t trong moi trng base, khi tang OH
(tng pH) se 0giam
tnh kh,
.059 hay
[ClOtang
4 ]
lai.
0.36
lg
(V )
ngc

[ClO3 ][OH ]

ANH HNG CUA pH VI CAC HP

CHAT CUA Mn

4. GIAN O FROST

Gian o Frost bieu dien s tng quan

gia G (thong qua ai lng nE tnh
bang V) va cac trang thai oxy hoa
cua nguyen to.

e thiet lap gian o, trc het ta tnh

gia tr nE cho tat ca cac cap X(N)/X(0)
(N la so oxy hoa cua nguyen to X). V
gian o phai lien tuc (linear) cho nen
can tnh ca trng hp X(N) khong
ben. V du sau cho Mn, la mot trong
nhng trng hp phc tap.

S dung gian o Frost

1. Nhan dang tac nhan kh va tac
nhan oxy hoa:

Hp chat nam pha tren la chat oxy hoa

oi vi chat nam ben trai cua chung.
Ngc lai, hp chat ben tren se la chat
kh oi vi chat ben phai cua chung.
Hoac da vao he so goc a cua cac oan
thang noi cac trang thai oxy hoa: Neu
a>0 th cau t cao hn la chat oxy hoa,
neu a<0 cau t cao hn la chat kh.

2. Nhan biet chat O-K manh hay yeu:

Da vao o doc cua oan noi cac hp
chat: o doc cang ln th tac nhan the
hien tnh oxy hoa (kh) cang manh.

3. Nhan biet san pham cua phan ng O-K:

Hp chat ay gian o co G nho, nen t co
kha nang phan ng. Nen hp chat ay
thng la san pham (ong hoc) cuoi cua qua
trnh O-K. Trong VD la Mn2+ trong moi trng acid va
Mn2O3 trong moi trng base.

4. Nhan biet qua trnh d ly:

Hp chat nam pha tren ng noi cua 2 cau t
lan can no se de b d ly thanh 2 hp chat lan
can o. VD trong moi trng base:
2MnO43- +2H2O MnO42- + MnO2 + 4OH-

5. Nhan biet qua trnh a hp:

Hp chat nam pha di ng noi cua 2 cau t
lan can no se de tao thanh t 2 hp chat lan
can o. VD trong moi trng acid: MnO 2 va Mn se
phan ng tao Mn2+.

IV. S ON NH CUA CAC CHAT

OXY HOA VA CHAT KH TRONG
MOI TRNG NC

Nc co the tham gia phan ng oxy

hoa kh vi vai tro la chat kh cua
O (-2) va vai tro chat oxy hoa cua H(+1).
Trong ieu kien cu the, chat nao co
the kh ln hn the kh cua cap
O2/H2O th co kha nang oxy hoa c
nc. Trai lai, chat nao co the kh
nho hn the kh cap H2O/H2 th co kha
nang kh c nc.

ieu kien on nh cua chat kh trong dung dch

nc

Chat kh

ieu kien khong tieu chuan, the kh cua cap 2H +/H2

25oC c tnh theo cong thc Nernst:

pH2
0,059

lg
0,0259 lg p H 2 0,059pH
2
2
[H 2 ]
0

Tnh oxy hoa cua nc trong cac ieu kien pH khac nhau
c the hien qua the kh :
Moi trng acid : (pH = 0)
2H+ + 2e H2
= 0,000V
Moi trng base: (pH =14)
2H2O + 2e H2 + 2OH-

= -0,83V

Moi trng trung tnh: (pH = 7)

2H2O + 2e H2 + 2OH-

= - 0,41V

Nh vay chat nao co the kh ln hn cac gia tr the

kh cho tren ieu kien pH xet la chat ben trong dung
dch nc.

Chat oxy hoa

ieu kien khong tieu chuan the kh cua
cap O2/H2O 25oC c tnh theo cong thc
Nernst:
[ H ]4 p

0,059
O2

lg
4
[ H 2 O ]2
0

Tnh kh cua nc cac moi trng khac nhau

the hien qua the kh:
Moi trng acid: (pH = 0)
O2(k) + 4H+ + 4e 2H2O = 1,23V
Moi trng base: (pH = 14)
O2 (k) + 2H2O + 4e 4OH- = 0,401V
Moi trng trung tnh (pH = 7):
O2(k) + 4H+ + 4e 2H2O = 0,815V
Nh vay chat nao co the kh nho hn the kh
cho tren ieu kien pH xet la chat ben trong
dung dch nc. (xem v du ve phan ng vi
nc)

So sanh kha nang phan ng khi s

dung cat (SiO2) va khi khong s dung
cat SiO2 trong phan ng hoan nguyen
quang phosphorite
Cac so lieu nhiet tao thanh chuan
va entropy chuan cua cac chat 250C
Ca3(PO4
)2
(n
ta)

0t,298
(kJ/mol)
S0298
(J/mol.K
)

C
(graphit
e)

SiO2
(thc
h
anh)

CaSiO3
CO
(tam (kh)
ta)

-4105

-912

-1635

+241

+6

+41

+82

110

P4
(tra
ng)

CaO
(lap
phng
)

-635

+19
+164
8

+43

Phan ng khong s dung cat:

2Ca3(PO4)2 + 10C = 6CaO + 10CO + P4

H 0pu , 298 (635 6 110 10 0) (0 4105 2) 3300kJ

S0pu , 298 (6 43 198 10 164) (2 241 10 6) 1860J / K
G 0pu ,1773 H 0pu , 298 1773 S0pu , 298 2,22kJ

Phan ng co s dung cat:

2Ca3(PO4)2 + 10C + 6SiO2 = 6CaSiO3 + 10CO +
P4

H 0pu , 298 (1635 6 110 10 0) (0 4105 2 912 6) 2772kJ

S0pu , 298 (6 82 198 10 164) (2 241 10 6 6 41) 1848J / K
G 0pu ,1773 H 0pu , 298 1773 S0pu , 298 504,5kJ

Nhan xet: Khi s dung cat th phan ng

xay ra thuan li hn rat nhieu v cat ong
vai tro acid lam tang kha nang oxy hoa
cua phosphorite (back)

V du: Xet xem chat nao trong cac

chat sau ve phng dien nhiet ong
hoa hoc co the ben trong dung dch
nc (khong co mat khong kh):
CoCl3, CrSO4, FeCl3 , KMnO4, Na2SO3.
Biet rang chung eu tan nhieu trong
nc.
The kh
tieu
chuan
trong
moi
trng
3+
2
3+
2
3+
2
2
Co /Co Cr /Cr Fe /Fe MnO4 /Mn SO42-/H2S
+
+
acid: +
+
O3

(V
)

1,84

0,77
-0,41
1

1,51

0,17

Giai:
So sanh vi cac gia tr the kh tieu chuan cua
nc chung ta co trong moi trng acid:
Chat kh:

* Na2SO3 ben v co = 1,17V > 0,000V;

* CrSO4 khong ben v co = -0,41V < 0,000V

2Cr2+ + 2H+ = 2Cr3+ + H2
Chat oxy hoa:

* FeCl3 ben v co = 0,771 V< 1,23V.

* CoCl3 khong ben v co = 1,84V > 1,23V

4 Co3+ + 2H2O = 4Co2+ + O2 + 4H+

* KMnO4 khong ben v co = 1,51V > 1,23V

Tuy nhien do van e ong hoc phan ng oxy
hoakh gia kali permanganat va nc thc te
khong dien ra ma xay ra s phan huy cham
cua ion permanganat trong nc:
4MnO4- + 4H+= 3O2 + 4MnO2 + H2O

The kh tieu chuan trong moi trng base:

MnO4-/MnO2 (=0,6V),
SO42-/SO32- (=-0,93V)
Trong moi trng base:
Chat kh:

* Na2SO3 khong ben v co = -0,93 < -0,83V

Tuy nhien phan ng kh nc giai phong
hydro cua ion sulfurous (SO32-) khong xay ra do
van e ong hoc.
Chat oxy hoa:
* KMnO4 khong ben v co = 0,6 > 0,401V
Tuy nhien do van e ong hoc phan ng oxy
hoakh gia kali permanganat va nc thc
te khong dien ra.

Cac chat con lai tao hydroxide t tan nen

khong ban en ay (chung khong con la
muoi na). (back)