Professional Documents
Culture Documents
4
2
ca phn t nit s2 *2
s x,y z : e1 v e2 u c bt ra t
MO-z (MO b chim cao nht).
z
2p
*
z
*
x
*
y
2pb
s*
2sa
2sb
s
FeSO4
Fe2(SO4)3 c
A (dd)
AgNO3
B kt ta trng
C kt ta xanh m
D kt ta trng
FeCl2
KMnO4, H+
E (dd)
Pb(OH)2, KOH
G kt ta xanh
A + F kt ta nu
(A)
(B)
(C)
(D)
Trang 1/8
(E)
2+
2 [Fe(CN)3 Fe3[Fe(CN)6]2 xanh
6 ] + 3 Fe
(G)
2+
Hoc K+ + [Fe(CN)3 KFe[Fe(CN)6] xanh
6 ] + Fe
42 [Fe(CN)36 ] + Pb(OH) 2 + 2 OH 2 [Fe(CN) 6 ] + 2 H2O + PbO2 nu
2. Cu hnh electron ca Fe2+ l [Ar]3d64s04p04d0
(F)
4s
4p
4d0
3d6
V CN- l phi t trng mnh, do khi to phc vi Fe2+, 4 electron c thn trn 4 obitan 3d
ca Fe(II) b ghp i, gii phng 2 obitan 3d trng. Hai obitan ny lai ha vi 1 obitan 4s v 3 obitan
4p, to thnh 6 obitan lai ha d2sp3 hng v 6 nh ca hnh bt din u. Mi obitan lai ha ny xen
ph vi mt obitan t do c hai electron ca CN -, to ra 6 lin kt cho nhn, hnh thnh phc
[Fe(CN)64- ] lai ha trong, c cu trc bt din. Phc ny nghch t v c tng spin bng khng:
CN- CN
CN
CN- CN- CN
d2sp3
+0,55
Cr(V)
+1,34
Cr(IV)
Ex
Cr3+
-0,408
Cr2+
Ey
Cr
-0,744
1. Tnh E 0x v E 0y .
2. Da vo tnh ton, cho bit Cr(IV) c th d phn thnh Cr3+ v Cr(VI) c khng?
3. Vit qu trnh xy ra vi h oxi ha kh Cr2 O 72- /Cr3+ v tnh bin thin th ca h nhit
298 K, khi pH tng 1 n v pH.
4. 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? V sao? Ghi s oxi ha tng ng trn mi nguyn t.
0
Cho: E Cr O2- /Cr3+ = 1,33 V; Hng s kh R = 8,3145 J.K1.mol1; Hng s Faraay F = 96485 C.mol1.
2 7
Hng dn gii:
1. T gin ta c: 3.(-0,744) = -0,408 + 2 E 0y E 0y = -0,912 (V)
0,55 + 1,34 + E 0x 3.0,744 = 6.0,293 E 0x = +2,1 (V)
2. Cr(IV) c th d phn thnh Cr3+ v Cr(VI) khi G0 ca qu trnh < 0.
2Cr(IV) + 2 e 2Cr3+ (1) E10 = E 0x = 2,1 V G10 = -n E10 F = - 2.2,1.F
0,55 + 1,34
Cr(VI) + 2 e Cr(IV) (2) E 02 =
= 0,945 (V) G 02 = -n E 02 F = - 2.0,945.F
2
T (1) v (2) ta c: 3Cr(IV) 2Cr3+ + Cr(VI)
G 30
G 30 = G10 - G 02 = - 2.(2,1 - 0,945).F < 0 Vy Cr(IV) c d phn.
3.
Trang 2/8
E1 = 1,33 +
0
0
pK a(CH3COOH) = 4,76; ES/H
= 0,14 V; E O2 /H 2O =1,23 V; 25 oC: 2,303
2S
Hng dn chm:
1. Gi nng ca Na2S v CH3COONa trong dung dch A
Na3PO4, trong dung dch xy ra cc qu trnh:
S2+ H2O HS- + OHHS
+ H2O H2S + OHCH3COO- + H2O CH3COOH + OHH2O H+ + OHSo snh 4 cn bng trn tnh theo (1):
S2+ H2O HS- + OHC C1
[ ] C1- 10-1,5
10-1,5
10-1,5
RT
l n = 0,0592lg.
F
10-1,1
10-6,98
10-9,24
10-14
(1)
(2)
(3)
(4)
10-1,1
[HS- ] 101,5
=
= 0, 7153
CS20, 0442
Khi thm Na3PO4 vo dung dch A, ngoi 4 cn bng trn, trong h cn c thm 3 cn bng sau:
10-1,68
(5)
PO 3-4 + H2O HPO 2-4 + OH-
10-6,79
10
-11,85
(6)
(7)
[HS ]
[HS-] = 0,0442. 0,57224 = 0,0253 (M).
CS2-
H2 S
0,884
37, 68
0,884
0, 01.20
= 0,02346 (M) v CH3COO-:
= 5,308.10-3 (M).
37, 68
37, 68
Cc qu trnh:
H2S H+ + HS10-7,02
(8)
+
2-12,9
HS H + S
10
(9)
H2O H+ + OH10-14
(10)
-9,24
CH3COO + H2O CH3COOH + OH 10
(11)
pH ca h c tnh theo (8) v (11):
107,02.[H 2S]
h = [H+] = [HS-] [CH3COOH] =
- 104,76. [CH3COO-].h
h
H thu c gm H2S:
h =
(12)
Chp nhn [H2S]1 = CH2S = 0,02346 (M) v [CH3COO-]1 = CCH COO- = 5,308.10-3 (M), thay vo
3
2x
K 2 = 104E2 / 0,0592
0
K = 104(E2 E1 ) / 0,0592
0
S + 2H + 2e H2S
H2S 2H+ + S2+
K 3 = 102E3 / 0,0592
Ka1.Ka2 = 10-19,92
0
O2 + 2H2O + 4e 4OH-
K 2 = 104E 2 / 0,0592
0
pK a3 + pK a2
= 9,765 dung dch Na3PO4 lm ch th metyl chuyn
2
mu vng.
pK a1 + pK a2
= 4,68 5,00 ch th metyl c mu hng da cam trong dung dch
2
NaH2PO4. Vy c th dung metyl phn bit 3 dung dch trn.
pH (NaH 2 PO4 )
Kp
P0n (k)
K p1
P0
K p1
1,000.105
4, 720.104
= 0,472
1,000.105
K p2
P0
K p2
1,000.105
1, 280.104
= 0,128
1,000.105
1,000.105
1
vi pO2 l p sut cn bng ca oxi p O2 =
= 10,87 (Pa)
9200,38
p O2
102. CA (mol/L)
102. CB (mol/L)
1,2
1,0
0,6
0,5
0,3
0,15
0
10
20
30
40
t (pht)
0,25
0,125
0
20
40
60
t (pht)
Trang 6/8
Hnh 1
Hnh 2
1. 25 oC hng s cn bng ca phn ng (a) l KC = 4.106. Tnh thi gian cn thit h t n
trng thi cn bng, nu C0A = C0B = 1,00 M v Cx = 1,00 M khng thay i; lc u trong h cha c
mt cc sn phm ca phn ng.
2. 80 oC hng s cn bng ca phn ng (a) l KC = 1.105. Tnh H v S ca phn ng (a) v cho
bit thi gian cn thit t n cn bng s tng hay gim (coi s ph thuc ca H v S vo nhit
l khng ng k)?
3. Ngi ta cho rng c ch phn ng (a) din ra qua 3 giai on s cp sau:
k5
k3
k1
AXB
C + D + X (d)
AX (b)
AXB (c)
A + X
AX + B
k2
k4
(2)
v = k'. C .
T hnh 1 rt ra thi gian phn ng mt na (t1/2) khng ph thuc vo nng u ca A v t1/2 =
ln2 0, 693
10 (pht) a = 1v k' =
= 6,93.10-2 (pht-1)
=
t1/2
10
a
A
Tng t trong th nghim 2, do C0A = 3,00 M (rt d) k. (C0A )a . C Xx = const = k'' v = k''. C bB .
T hnh 2 thi gian phn ng mt na khng ph thuc vo nng u ca B b = 1.
Biu thc ca nh lut tc (1) tr thnh:
v = k.CA.CB. C Xx = kap.CA.CB.
vi kap l hng s tc biu kin ca phn ng v kap=k. C Xx
Nh vy phn ng s din ra theo quy lut ng hc bc 2.
k' 6,93.102
T (2) ta c: kap = k. C Xx = 0 =
= 0,01155 L/(mol.pht)
CB
6, 00
X
Xt phn ng:
A + B
Kc = 4.106
C + D
C0
2.
1
1
0
0
C
x
x
1-x 1-x
2
(1-x)
KC =
= 4.106 x 5.10-4 (M)
x2
V phn ng l bc 2 v C0A = C 0B = 1,00 M nn phng trnh ng hc tch phn c dng:
1 1
1
1
- 0 = kap.t
= 0,01155.t t = 1,73.105 pht.
4
C C
5.10
1
Vy nhit 25 oC cn ti 1,73.105 pht phn ng t c cn bng.
G 0298,15 = - 8,3145 . 298,15 . ln(4.10 6 ) = - 37684,8 (J/mol)
0
G 353,15
= - 8,3145 . 353,15 . ln(1.105 ) = - 33805 (J/mol)
(3)
0
G 353,15
=
0
(4)
-33805 = H 353,15.S
0
Trang 7/8
Khi tng nhit t 25 oC ln 80 oC, tc phn ng thun v nghch u tng ln, thi gian cn
thit h t n cn bng s gim i.
3.
k5
k3
k1
AXB
C + D + X (d)
AXB (c)
AX (b)
AX + B
A + X
k4
k2
C AX =
--------------------------HT-----------------------
Trang 8/8