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CHNG 11

Phan ng oxy hoa kh (O K) Phan ng trong o co s trao oi electron gia cac nguyen t cua nhng nguyen to tham gia phan ng lam thay oi so oxy hoa cac nguyen to.

Qua trnh cho electron goi la qua trnh oxy hoa, chat cho electron goi la chat kh (chat b oxy hoa).  V du: Zn 2e ' Zn+2 Qua trnh nhan electron goi la qua trnh kh, chat nhan electron goi la chat oxy hoa.  V du: Cu+2 + 2e ' Cu

Ph n ng t ng quat: hI OxII ' OxI hII + ne ' hI + OxII ' + OxI ne +

Qt oxh: Qt kh: Pt oxh kh: KhII


Cap oxy hoa kh: OxI/KhI , OxII/KhII V du: Zn Cu2+ + 2e Zn + Cu2+ Zn + CuSO4 Zn2+/Zn; Cu2+/Cu ' ' Zn2+ Cu Zn2+ + Cu + 2e

Qt oxh: Qt kh: Pt oxh kh: Pt phan t:

ZnSO4 + Cu

Cap oxy hoa kh:

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.

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


X2

Cu+2 + 2e 2Al

X p Cu3

+ 3Cu+2 = 2Al+3

3Cu

2Al + 3CuSO4

p 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 p MnSO4  KNO3  K 2 SO4  H 2O


MnO   5e p Mn 2 4
 NO  2e p NO3 2
 MnO4  5e  8H  p Mn 2  4 H 2O

X2 X5

 NO2  2e  H 2O p NO3  2 H 

  2MnO 4  5NO 2  6H  ! 2Mn   5NO3  3H 2 O

2KMnO 4  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, OHvao 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 p K 2 CrO4  KCl  H 2 O


 ClO3  6e  3H 2 O ! Cl   6OH   Cr 3  3e  8OH  ! CrO42  4H 2 O

X1 X2

  ClO3  2Cr 3  OH  ! Cl   2CrO4 2  5H 2 O

KClO 3  2CrCl 3  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:

KMnO 4  KNO 2  H 2 O p MnO2  KNO 3  KOH


 MnO4  3e  2H 2 O ! MnO2  4OH    NO2  2e  H 2 O ! NO3  2H 

X2 X3

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

   2MnO4  3NO2  H 2 O ! 2MnO2  3NO3  2OH 

2KMnO 4  3KNO 2  H 2 O ! 2MnO 2  3KNO 3  2KOH

Phan ng O K va dong ien

ieu kien bnh thng, phan ng O K xay ra cung mot ni th hoa nang se bien thanh nhiet nang. ieu kien ac biet phan ng O K xay ra gian tiep hai ni khac nhau th hoa nang se bien thanh ien nang (qua day dan).eMang ngan e-

eCha Chat kh t oxh Cathode Anode

Nguyen to galvanic (1780):


 La thiet b chuyen hoa

nang sang ien nang. Cau tao gom hai thanh kim loai, nhung trong dung dch muoi cua no, noi vi nhau qua si day dan kim loai.
 Hai thanh kim loai nay mot

Luigi Galvani (Italia)

thanh co tnh kh manh hn (e cho e) mot thanh

Anode (-) , xay ra qua trnh oxy hoa

Cathode (+), xay ra qua trnh kh

ien cc kem: Zn 2e p Zn+2 goi la am cc (Cathode) ien cc ong: Cu+2 + 2e p Cu goi la dng cc (Anode) Tc la am cc xay ra qua trnh Oxy hoa, Zn la chat Kh. dng cc xay ra qua trnh kh, Cu la chat Ox. Phng trnh cua galvanic: Zn + Cu+2 = Zn+2 + Cu Ngi ta ky hieu nguyen to ganvanic: Hay

 Zn ZnSO4
 Zn Zn 2

CuSO4 Cu 
Cu2 Cu 

Tong quat:  M I ddM I ddM II M II 

The ien cc N (V), hay con goi la the Oxy hoa Kh, hay la ban the phan ng, la mot ai lng khong the o trc tiep, ma phai so sanh vi mot ien cc chuan. Ngi ta chon Hydro lam ien cc chuan: 2H+(dd) + 2e p H2 (k), ien cc la platinum. Quy c: N0H2 = 0 (V). (The ien cc tuyet oi cua no c chng 4.4 4.6 V)

Phng trnh Nernst: Kh ne p Ox, N


RT aOx ln N !N  nF a Kh
0

Vi a la hoat o. Hoat o cua cac kim loai tinh khiet (va ca long tinh khiet) coi nh bang 1. Vi dung dch that (s dung C) nhiet o 298K, ta co (R=8.31, T=298,F=96500):

0.059 [Ox] N !N  lg n [ Kh]


0 0

N phu thuoc vao ban chat chat tham gia qua trnh ien cc (N0, n) nhiet o T, nong o chat tham gia qua trnh ien cc C. Ta co: UG = -nFN, hay UG0 = -nFN0 Sau ay la bang the ien cc tieu chuan cua mot so ban phan ng (The Ox-Kh).

Ban phan ng 1bar, 298K, Ci = 1M


Li+(aq) + e K+(aq) + e Ba2+(aq) Ca2+(aq) Na+(aq) + + 2e 2e Li(s) K(s) Ba(s) Ca(s) Na(s) Mg(s) Be(s) Al(s) Ti(s) Mn(s) SnH4(g)

N0

(V)

Zn2+(aq) + 2e Cr3+(aq) + 3e Fe2+(aq) + 2e Cr3+(aq) + e Sn2+(aq) + 2e 2H+(aq) + 2e Sn4+(aq) + 2e Cu2+(aq) + e

Zn(s) Cr(s) Fe(s) Cr2+(aq) Sn(s) H2(g) Sn2+(aq) Cu+(aq)

0.76 0.74 0.44 0.42 0.13 0.00 +0.15 +0.16 +0.17 +0.34

3.05 2.93 2.91 2.76 2.71 2.38 1.85 1.68 1.21 1.18 1.07 0.83

Mg2+(aq) + 2e Be2+(aq) + 2e Al3+(aq) + 3e Ti3+(aq) + 3e Mn2+(aq) + 2e Sn(s) + 4H+ + 4e

SO42(aq) + 4H+ + 2e 2H2O(l) + SO2(aq) Cu2+(aq) + 2e Cu(s)

O2(g)+2H2O(l)+4e SO2(aq)+4H++4e Cu+(aq) + e

4OH(aq) +0.40 S(s)+ 2H2O +0.50 +0.52 +0.54

Cu(s) 2I(aq)

2 H2O(l)+2e

H2(g)+2OH(aq)

I2(s) + 2e

MnO4(aq) + 2H2O(l) + 3e MnO2(s) + 4 OH(aq) S2O3 + 3H2O O2(g) +


2

+0.59 +0.60 +0.70 +0.77 +0.80 +0.80 +0.80 +0.85 +0.90 +0.91 +0.95

Br2(aq) + 2e

2Br(aq) I2(s)

+1.09 +1.20 +1.20 +1.23 +1.23 +1.36 +1.36 +1.51 Cl2(g) +1.63 +1.70

6H+

4e

2S(s) + H2O2(aq)

2IO3(aq) + 12H+ + 10e + 6H2O ClO4(aq) + 2H+ + 2e ClO3(aq) + H2O O2(g) + 4H+ + 4e MnO2(s) + 4H+ + 2e Mn2+(aq) + 2H2O Cl2(g) + 2e 2Cl(aq) 2H2O

2H+ +

2e

Fe3+(aq)

Fe2+(aq) 2Hg(l) Ag(s)

Hg22+(aq) + 2e Ag+(aq) + e

NO3(aq) + 2H+(aq) +e NO2(g) + H2O(l) Hg2+(aq) + 2e Hg(l)

Cr2O72(aq) + 14H+ + 6e 2Cr3+(aq) + 7H2O MnO4(aq) + 8H+ + 5e Mn2+(aq) + 4H2O 2HClO(aq) + 2H+ + 2e + 2H2O MnO4(aq) + 4H+ + 3e MnO2(s) + 2H2O H2O2(aq) + 2H+ + 2e 2H2O

MnO4(aq) + H+ + e HMnO4(aq) 2Hg2+(aq) + 2e MnO2(s) + + 2H2O 4H+ + Hg22+(aq) e Mn3+(aq)

+1.76

The hieu cc ai xuat hien gia hai c c c a nguyen to ganvanic goi la sc ien ong cua nguyen to ganvanic, khi ma nguyen to galvanic hoat ong T N.

 K hieu:

E ! N  N

Sc ien ong tieu chuan cua nguyen to galvanic. E0 o p = 1 atm, CM 0 0 0 (hay a) = 1, 298K. E ! N   N 

aKh1 + bOXH2 ' cOXH1 + dKh2 -(G = A = nFE


c OXH1 Kh d 2 (G ! (G 0  RT ln a Kh1 OXH b 2

c OXH1 Kh d 2  nFE ! RT ln K  RT ln a b Kh1 OXH 2


c RT RT OXH1 Kh d 2 E! ln K  ln a b nF nF Kh1 OXH 2

RT E ! ln K nF
0

RT OXH Kh ln E!E  nF Kh1a OXH


0

c 1

d 2 b 2

(G0

-nFE0

E ! E

RT sp ln  nF cd

V du vi phan ng trong nguyen to galvanic: Zn + Cu+2 = Zn+2 + Cu RT CZn 2 0 ECu / Zn ! ECu / Zn  ln 2 F CCu 2 Vi N+ la cua cap Cu+2/Cu va N- la cua cap Zn+2/Zn, ta co

0 Cu / Zn

! N  N ! 0.337   0.763 ! 1.1V


0  0 

4 Xet phan ng:   Fe 2 Ce 3  Fe3 Ce

c tao thanh bi 2 ban phan ng sau

Ce  e Ce 3  2 Fe  e Fe

4

3

No=1.700V No=0.767V

V No cua cerium ln hn nen no la chat Oxy hoa. Ta co


o o E o ! N  - N  ! 1.700 - (0.767)

Trong nguyen to galvanic co:

RT [Fe3 ][Ce3 ] 0 0 E ! N - N- ! N - N  ln nF [Fe 2 ][Ce 4 ]


Tai can bang, E = 0 va:

RT [Fe ][Ce ] o N -N ! ln ! .05916 v log K , 25 C 2 4 F [Fe ][Ce ]


o  o 

3

3

K } 1016

Xet cac cap O-K: Ox1/Kh1 , Ox2/Kh2 Kh1 ' Ox1 + ne , N1 Kh2 ' Ox2 + ne , N2 Khi tron cac cap nay, se co phan ng:

Kh1 + Ox2 ' Ox1 + Kh2


Phan ng xay ra theo chieu thuan khi:

(G ! nFE2 / 1 !  nF 2  N1 0 N 2 " N1 N

Quy tac xet chieu phan ng:


 Phan ng O K xay ra theo chieu

dang Ox cua cap O K co N ln hn se Ox dang Kh cua cap O K co N nho hn.

 Thc te co the dung N0 e xet.

Nhng khi N0+ - N0- be qua th phai tnh toan tren N.

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