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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
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
ZnSO4 + Cu
Nguyen tac 1:
Tong so electron cho cua chat kh
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.
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).
V du:
X2 X5
NO2 2e H 2O p NO3 2 H
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:
X1 X2
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.
V du:
X2 X3
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-
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
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
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)
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):
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).
N0
(V)
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
Cu(s) 2I(aq)
2 H2O(l)+2e
H2(g)+2OH(aq)
I2(s) + 2e
+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)
Hg22+(aq) + 2e Ag+(aq) + e
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
+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
RT E ! ln K nF
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
Ce e Ce 3 2 Fe e Fe
4
3
No=1.700V No=0.767V
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:
(G ! nFE2 / 1 ! nF 2 N1 0 N 2 " N1 N