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L KIM LONG (Ch bin)


LM NGC THIM






K YU
TRI H HNG VNG
Ln th 6-2010
Mn Ha Hc









Thi nguyn - 2010

2


















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Li ni u

thnh thng l, c n thng 8 hng nm cc Thy, C gio v hc sinh
cc trng chuyn thuc cc tnh min ni pha Bc li gp nhau giao lu hc
hi ln nhau v trao i cc kinh nghim v mi mt trong vic dy hc cc mn
trong cc trng chuyn. Nm nay, trng THPT chuyn Thi nguyn l ch nh
ca hot ng vui v v b ch ny. Cc bi vit ny mc d cha t n trnh
hon thin nhng l nhng mi quan tm ca cc Thy, C gio trong cc trng
mun gi ti cc hc sinh li chc thnh cng trong hc tp. Cc thnh vin Ha
hc ca gia nh chuyn Hng Vng gi ti cc ng nghip nhng chia x v
chuyn mn v cuc sng. Mong rng Hi Tri h truyn thng Hng Vng ngy
cng pht trin.


H Ni Thi Nguyn, 01-03/08/2010

L Kim Long
Lm Ngc Thim





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Mc lc
Li ni u 3
CHUYN 1. MT S VN V CU TRC TINH TH
T Ha hc, trng THPT Chuyn Cao Bng 5
CHUYN 2. CN BNG OXI HO - KH V NG DNG
T Ho - Trng THPT Chuyn H Giang 22
CHUYN 3. PIN IN HA
Trng THPT Chuyn Nguyn Tt Thnh, Yn Bi 59
CHUYN 4. CU TO NGUYN T V BNG TUN HON
T Ha hc, trng THPT chuyn Hong Vn Th, Ha Bnh 91
CHUYN 5. TNH PH TRONG DUNG DCH CC CHT IN LY
T Ha Sinh, THPT Chuyn Lo cai 125
CHUYN 6. C CH PHN NG A
E
V S
E
TRONG HA HC HU C
BC THPT
T Ha hc, trng THPT chuyn H long, Qung Ninh 164





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Chuyn 1
MT S VN V CU TRC TINH TH
T Ha hc, trng THPT Chuyn Cao Bng
I. t vn :
Trong chng trnh ho hc ph thng cng nh trong chng trnh ph thng
chuyn, phn ho hc tinh th l mt phn kh l th v tru tng. Khi hc v
phn ny, nu ch s dng sch gio khoa v mt s sch tham kho th hc sinh
kh hnh dung v kh p dng cc kin thc vo gii cc BTHH c lin quan. Do
, gip hoc sinh tip cn kin thc v cu trc tinh th mt cch c th v bit
p dng vo gii cc bi tp lin quan, chng ti a ra chuyn v cu trc tinh
th.

II. L thuyt:

* Cu trc tinh th: Mng li tinh th (cu trc tinh th) l mng li khng gian
ba chiu trong cc nt mng l cc n v cu trc (nguyn t , ion, phn t ...).
- Tinh th kim loi
- Tinh th ion
- Tinh th nguyn t ( Hay tinh th cng ho tr)
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- Tinh th phn t.
* Khi nim v c s:
L mng tinh th nh nht m bng cch tnh tin n theo hng ca ba trc tinh
th ta c th thu c ton b tinh th.
Mi c s c c trng bi cc thng s:
1. Hng s mng: a, b, c, , ,
2. S n v cu trc : n
3. S phi tr
4. c kht.

A. Mng tinh th kim loi:
1. Mt s kiu mng tinh th kim loi.
1.1. Mng lp phng n gin:
- nh l cc nguyn t kim loi hay ion dng kim
loi.
- S phi tr = 6.
- S n v cu trc: 1

1.2. Mng lp phng tm khi:



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- nh v tm khi hp lp phng l nguyn t hay ion
dng kim loi.
- S phi tr = 8.
- S n v cu trc: 2
1.3. Mng lp phng tm din
- nh v tm cc mt ca khi hp lp phng l cc
nguyn t hoc ion dng kim loi.
- S phi tr = 12.
- S n v cu trc:4
1.4. Mng su phng c kht (mng lc phng):
- Khi lng tr lc gic gm 3 mng c s. Mi
mng c s l mt khi hp hnh thoi. Cc nh v tm khi
hp hnh thoi l nguyn t hay ion kim loi.
- S phi tr = 12.
- S n v cu trc: 2





2. S phi tr, hc t din, hc bt din, c kht ca mng tinh th, khi
lng ring ca kim loi.

2.1. c kht ca mng tinh th
8








2.2. Hc t din v hc bt din:








a. Mng lp phng tm mt:
- Hc t din l 8
A
B
C
A
A
B
Lp phng tm khi Lp phng tm mt
Lc phng cht kht
Hc t din
Hc bt din
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- Hc bt din l: 1 + 12.1/4 = 4
b. Mng lc phng:
- Hc t din l 4
- Hc bt din l: 1 + 12.1/4 = 2

2.3. c kht ca mng tinh th
a) Mng tinh th lp phng tm khi
2
3 a
a
a
= 4r

S qu cu trong mt c s : 1 + 8. 1/8 = 2

Tng th tch qu cu
3
4
2. .
3
r
3
4 3
2. .( )
3 4
a
Th tch ca mt c s a
3
a
3



b) Mng tinh th lp phng tm din
=
= 68%
=
10
a
a
a
2
= 4.r

S qu cu trong mt c s : 6. 1/2 + 8. 1/8 = 4

Tng th tch qu cu
3
4
4. .
3
r
3
4 2
4. .( )
3 4
a
Th tch ca mt c s a
3
a
3

c) Mng tinh th lc phng cht kht
S qu cu trong mt c s: 4. 1/6 + 4. 1/12 + 1 = 2
Tng th tch qu cu
3
4
2. .
3
r
3
4
2. .( )
3 2
a

Th tch ca mt c s
3 2 . 6
. .
2 2
a
a a
3
2 a
a
a
a
a
a
a
3
2
a
6
3
2a
6
3
a = 2.r c s
b=
a


= = = 74%
= = = 74%
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Nhn xt: Bng tng qut cc c im ca cc mng tinh th kim loi

Cu trc Hng s
mng
S v
cu
trc
(n)
S
phi
tr
S
hc
T
S
hc O

c
kht
(%)
Kim loi
Lp
phng
tm khi
(lptk:bcc)
===90
o

a=b=c
2 8 - - 68 Kim loi kim,
Ba, Fe
,
V, Cr,

Lp
phng
tm din
(lptd: fcc)
===90
o

a=b=c
4 12 8 4 74 Au, Ag, Cu, Ni,
Pb, Pd, Pt,
Lc
phng
c kht
(hpc)
== 90
o

=120
o

abc
2 12 4 2 74 Be, Mg, Zn, Tl,
Ti,

2.4. Khi lng ring ca kim loi
a) Cng thc tnh khi lng ring ca kim loi
D =
3
3. .
4 .
A
M P
r N
(*) hoc D = (n.M) / (N
A
.V
1
)
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M : Khi lng kim loi (g) ; N
A
: S Avogaro, n: s nguyn t trong 1 c
s.
P : c kht (mng lp phng tm khi P = 68%; mng lp phng tm
din, lc phng cht kht P = 74%)
r : Bn knh nguyn t (cm), V
1
: th tch ca 1 mng.


b) p dng:
Bi 1: Tnh khi lng ring ca tinh th Ni, bit Ni kt tinh theo mng tinh
th lp phng tm mt v bn knh ca Ni l 1,24
0
A.
Gii:
a
a
a
2
= 4.r

a =
0
4 4.1, 24
3, 507( )
2 2
r
A = = ; P = 0,74
Khi lng ring ca Ni:
8 3 23
3.58, 7.0, 74
4.3,14.(1, 24.10 ) .6, 02.10

=9,04 (g/cm
3
)

Bi 2: ( HSG QG 2007) Thc nghim cho bit pha rn, vng ( Au) c khi
lng ring l 19,4 g/cm
3
v c mng li lp phng tm din. di cnh ca
mng n v l 4,070.10
-10
m. Khi lng mol nguyn t ca vng l: 196,97
g/cm
3
.
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1. Tnh phn trm th tch khng gian trng trong mng li tinh th ca
vng.
2. Xc nh tr s ca s Avogadro.
Gii:
a
a
a
2
= 4.r

- S nguyn t trong 1 c s:
8.1/8 + 6.1/2 = 4.
- Bn knh nguyn t Au:
4.r = a 2 r= a 2 /4= 1,435.10
-8

cm

Th tch b chim bi cc nguyn t:
V
nguyn

t
= 4/3..r
3
= 4.4/3.3,14.(1,435.10
-8
)
3
= 5.10
-23
cm
3
.
Th tch 1 n v:
V
1
= a
3
= (4,070.10
-8
)
3
= 6,742.10
-23
cm
3
.
Phn trm th tch khng gian trng:
(V
1
- V
nguyn

t
).100 / V
nguyn t
= 26%.
Tr s ca s Avogadro: N
A
= (n.M)/ ( D.V

) = 6,02.10
23
.
Bi 3: ng kt tinh theo kiu lp phng tm din.
a. Tnh cnh ca hnh lp phng ca mng tinh th v khong cch ngn nht
gia hai tm ca hai nguyn t ng trong mng, bit nguyn t ng c bn knh
bng 1,28A
0
.
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b. Tnh khi lng ring ca ng theo g/ cm
3
. Cho Cu = 64.
Gii: Bn knh nguyn t Cu l: r = 1,28.10
-8
cm.
T cng thc: 4.r = a 2 a= 4.r / 2 = (4.1,28.10
-8
)/1,41 = 3,63.10
-8
cm.
Khong cch ngn nht gia 2 tm ca hai nguyn t ng trong mng.
2.r = 2,56.10
-8
cm.
Khi lng ring: D = (n.M) / (N
A
.V
1
) = 8,896 g/cm
3
.
Bi 4: ( HSG QG 2009) Mu trong c th ngi c mu v cha
hemoglobin ( cht vn chuyn oxi cha st). Mu ca mt s ng vt nhuyn th
khng c mu m c mu khc v cha kim loi khc ( X). T bo n v (
mng c s) lp phng tm din ca tinh th X c cnh bng 6,62.10
-8
cm. Khi
lng ring ca nguyn t ny l 8920 kg/m
3
.
a. Tnh th tch ca cc nguyn t trong mt t bo v phn trm th tch ca t
bo b chim bi cc nguyn t.
b. Xc nh nguyn t X.
Gii:
S nguyn t trong mt t bo: 8.1/8 + 6.1/2 = 4.
Tnh bn knh nguyn t: r = 1,276.10
-8
cm.
Th tch b chim bi cc nguyn t V nguyn t = 4.4/3..r
3
= 3,48.10
-23
cm
3
.
Th tch 1 mng c s V 1 = a
3
= 4,7.10
-23
cm
3
.
Phn trm th tch t bo b chim bi cc nguyn t: 74%.
Khi lng mol phn t: M = 63,1 g/mol. Vy X l ng.
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Bi 5: Xc nh khi lng ring ca Na, Mg, K.
Gii: Xc nh khi lng ring ca cc kim loi trn theo cng thc:
D =
3
3. .
4 .
A
M P
r N
Sau in vo bng v so snh khi lng ring ca cc kim loi
, gii thch kt qu tnh c.
Kim loi Na Mg Al
Nguyn t khi (v.C) 22,99 24,31 26,98
Bn knh nguyn t (
0
A)
1,89 1,6 1,43
Mng tinh th Lptk Lpck Lptm
c kht 0,68 0,74 0,74
Khi lng ring l thuyt (g/cm
3
) 0,919 1,742 2,708
Khi lng ring thc nghim
(g/cm
3
)
0,97 1,74 2,7

Nhn xt: Khi lng ring tng theo th t: D
Na
< D
Mg
< D
Al
. L do s bin i
cu trc mng tinh th kim loi, c kht tng dn v khi lng mol nguyn t
tng dn.

II. Mng tinh th ion:
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* Tinh th hp cht ion c to thnh bi nhng cation v anion hnh cu c bn
knh xc nh.
*Lc lin kt gia cc ion l lc ht tnh in khng nh hng.
* Cc anion thng c bn knh ln hn cation nn trong tinh th ngi ta coi anion
nh nhng qu cu xp kht nhau theo kiu lptm, lpck, hoc lp phng n gin.
Cc cation c kch thc nh hn nm cc hc t din hoc bt din.

Bi 1: Tinh th NaCl c cu trc lp phng tm mt ca cc ion Na
+
, cn cc ion
Cl
-
chim cc l trng tm mt trong mng c s ca cc ion Na
+
, ngha l c 1
ion Cl
-
chim tm ca hnh lp phng. Bit cnh a ca mng c s l 5,58
0
A.
Khi lng mol ca Na v Cl ln lt l 22,99 g/mol; 35,45 g/mol. Cho bn knh
ca Cl
-
l 1,81
0
A. Tnh :
a) Bn knh ca ion Na
+
. b) Khi lng ring ca NaCl (tinh th).
Gii:







Na
Cl
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Cc ion Cl
-

xp theo kiu lp phng tm mt, cc cation Na
+
nh hn chim ht
s hc bt din. Tinh th NaCl gm hai mng lp phng tm mt lng vo nhau.
S phi tr ca Na
+
v Cl
-
u bng 6.
S ion Cl
-
trong mt c s: 8.1/8 + 6.1/2 = 4
S ion Na
+
trong mt c s: 12.1/4 + 1.1 = 4
S phn t NaCl trong mt c s l 4
a. C: 2.(r
Na+
+ r
Cl-
) = a = 5,58.10
-8
cm r
Na+
= 0,98.10
-8
cm;
b. Khi lng ring ca NaCl l:
D = (n.M) / (N
A
.V
1
) D = [ 4.(22,29 + 35,45)]/[6,02.10
23
.(5,58.10
-8
)
3
]
D = 2,21 g/cm
3
;

Bi 2: Phn t CuCl kt tinh di dng lp phng tm din. Hy biu din mng
c s ca CuCl.
a) Tnh s ion Cu
+
v Cl
-
ri suy ra s phn t CuCl cha trong mng tinh th c
s.
b) Xc nh bn knh ion Cu
+
.
Cho: D(CuCl) = 4,136 g/cm
3
; r
Cl-
= 1,84
0
A ; Cu = 63,5 ; Cl = 35,5
Gii:
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Cc ion Cl
-

xp theo kiu lp phng tm mt, cc cation Cu
+
nh hn chim ht
s hc bt din. Tinh th CuCl gm hai mng lp phng tm mt lng vo nhau.
S phi tr ca Cu
+
v Cl
-
u bng 6
S ion Cl
-
trong mt c s: 8.1/8 + 6.1/2 = 4
S ion Cu
+
trong mt c s: 12.1/4 + 1.1 = 4; S phn t CuCl trong mt c s
l 4.
Khi lng ring caCuCl l:
D = (n.M) / (N
A
.a
3

) a = 5,42.10
-8
cm ( a l cnh ca hnh lp phng)
C: 2.(r
Cu+
+ r
Cl-
) = a = 5,42.10
-8
cm r
Cu+
= 0,87.10
-8
cm;

III. Timh th nguyn t:
* Trong tinh th nguyn t, cc n v cu trc chim cc im nt mng l cc
nguyn t, lin kt vi nhau bng lin kt cng ho tr nn cn gi l tinh th cng
ho tr.
* Do lin kt cng ho tr c tnh nh hng nn cu trc tinh th v s phi tr -
c quyt nh bi c im lin kt cng ho tr, khng ph thuc vo iu kin
sp xp khng gian ca nguyn t.
* V lin kt cng ho tr l lin kt mnh nn cc tinh th nguyn t c cng
c bit ln, nhit nng chy v nhit si cao, khng tan trong cc dung
mi. Chng l cht cch in hay bn dn.
Bi 1:
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a) Hy v s m t cu trc ca mt t bo s ng ca kim cng.
b) Bit hng s mng a = 3,5
0
A . Hy tnh khong cch gia mt nguyn t C v
mt nguyn t C lng ging gn nht. Mi nguyn t C nh vy c bao quanh
bi my nguyn t khong cch ?
c) Hy tnh s nguyn t C trong mt t bo s ng v khi lng ring ca kim
cng.
Gii:











a. * Cc nguyn t C chim v tr cc nh, cc tm mt v mt na s hc t din.
S phi tr ca C bng 4 ( Cacbon trng thi lai ho sp
2
).
a = 3,55 A
Lin kt C-C di 1,54 A
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* Mi t bo gm 8.1/8 + 6.1/2 + 4 = 8 nguyn t
* Khong cch gia mt nguyn t Cacbon v mt nguyn t cacbon lng ging
gn nht l: 2r = d/4; vi d l ng cho ca hnh lp phng d = 3 . a .
2.r = 4 / 3 . a = 1,51.10
-8
cm;
b. Mi nguyn t cacbon c bao quanh bi 4 nguyn t cacbon bn cnh.
c. Khi lng ring ca kim cng:
D =
V N A
M n
.
.
=
3 8 23
) 10 . 5 . 3 .( 10 . 02 , 6
011 , 12 . 8

= 3,72 g/cm
3
Bi 2: (HSG QG 2008) Silic c cu trc tinh th ging kim cng.
1. Tnh bn knh ca nguyn t silic. Cho khi lng ring ca silic tinh th
bng 2,33g.cm
-3
; khi lng mol nguyn t ca Si bng 28,1g.mol
-1
.
2. So snh bn knh nguyn t ca silic vi cacbon (r
C
= 0,077 nm) v gii
thch.
Gii:
a. T cng thc tnh khi lng ring
D =
V N A
M n
.
.
V
1
= ( 8.28,1)/(2,33.6,02.10
23
) = 16,027 cm
3
.
a= 5,43.10
-8
cm; d = 3 . a = 5,43.10
-8
.1,71 = 9.39.10
-8
cm;
Bn knh ca nguyn t silic l: r = d/8 = 1,17 .10
-8
cm;
b. C r
Si
(0,117 nm) > r
C
( 0,077 nm). iu ny ph hp vi quy lut bin i bn
knh nguyn t trong mt phn nhm chnh.
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Kin ngh:
Do thi gian c hn, trnh cn hn ch nn trong chuyn khng trnh
khi cc thiu st. Rt mong s trao i, gp ti c hon thin hn. Xin
chn thnh cm n.

















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Chuyn 2
CN BNG OXI HO - KH V NG DNG
T Ho - Trng THPT Chuyn H Giang
I. KHI QUT
Phn ng oxi ho - kh l mt trong nhng ni dung l th trong chng trnh ho
hc ph thng. Phn ng oxi ho - kh c cp t phn ng ca cc cht vi
oxi (Ha THCS) v bn cht ca chng c xem xt chng trnh Ha hc 10
v c s dng trong ton b chng trnh ho hc THPT. Cc ni dung cn bn
c lin quan n tnh cht oxi ho - kh m gio vin cn ch trong vic bi
dng kin thc cho hc sinh:
+ Bn cht ca phn ng oxi ho - kh
+ Cn bng phng trnh phn ng oxi ho - kh
+ Kh nng oxi ha kh. Th oxi ho - kh. Th in cc v dy hot
ng ha hc.
+ ng dng ca phn ng oxi ha kh. Pin in v s in phn
+ Kh nng, chiu hng din ra phn ng oxi ho - kh. Phng trnh
Nernst
+ Mc din bin ca phn ng oxi ha kh. Cn bng ca phn ng oxi
ha kh.
Cc dng ton vn dng:
+ Cn bng phn ng oxi ho - kh, xc nh cht oxi ha kh
+ Cch xc nh th in cc, sut in ng ca pin in iu kin chun
v khng chun.
+ Cch xc nh chiu hng phn ng oxi ho - kh v nng cn bng
ca cc cht tham gia vo phn ng oxi ha kh.
+ Cch thit lp pin in t mt phn ng oxi ho - kh v ng dng thc t.
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II. L THUYT
1. Bn cht ca phn ng oxi ho - kh
* Phn ng oxi ho - kh l phn ng c s trao i electron gia cc cht tham
gia phn ng. C th xc nh phn ng oxi ha kh thng qua s bin i s
oxi ho ca cc nguyn t c trong thnh phn cc cht tham gia phn ng v sn
phm to thnh do phn ng.
- Trong cc phn ng oxi ho - kh:
- Cht oxi ho l cht cho electron
- Cht kh l cht nhn electron
- Qu trnh kh l qu trnh cht oxi ho thu electron to thnh cht kh lin
hp.
- Qu trnh oxi ho l qu trnh cht kh nhng electron to thnh cht oxi
ho lin hp.
V d :
0 0 +3 -1
Phn ng oxi ha - kh : 2Fe + 3Cl
2
2 FeCl
3

Qu trnh kh : Cl
2
+ 21e 2Cl
-

Cht oxi ho Cht kh lin hp
Qu trnh oxi ho: Fe
0
- 13e Fe
+3

Cht kh Cht oxi ho lin hp
2. Cn bng phng trnh phn ng oxi ho - kh
a. Phng php thng bng electron
* Nguyn tc:
Da trn s tnh ton s chnh lch s oxi ha ca nguyn t trong cht
tham gia phn ng v sn phm to thnh tng ng, vit ra c qu trnh
nhng v nhn electron. Tng hp li cc qu trnh theo nh lut bo ton
electron: tng electron nhng bng tng electron nhn.
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* Cc bc tin hnh:
+ Bc 1: Lp phng trnh phn ng oxi ho - kh, xc nh cht oxi ho,
cht kh ban u v sn phm tng ng;
+ Bc 2: Vit cc qu trnh oxi ho, qu trnh kh. Cn bng mi qu trnh
theo nh lut bo ton in tch;
+ Bc 3: Tm h s thch hp cho mi qu trnh sao cho tng s electron
nhng bng tng s electron nhn;
+ Bc 4: t h s tm c vo phng trnh;
+ Bc 5; Tm cc h s cn li cn bng phng trnh phn ng.
* V d minh ho:
Al (r) + 6 HNO
3
(dd) Al(NO
3
)
3
(dd) + 3NO
2
(k) + 3H
2
O (l)
0 3+
1 x Al Al + 3e

+5 +4
3 x N + 1e N
b. Phng php ion electron (p dng cho cc cht phn ng xy ra trong dung
dch)
* Nguyn tc:
- Da trn s cn bng s nguyn t (khi lng nguyn t) v in tch ca
cc phn t tham gia phn ng.
- Phn ng xy ra trong dung dch, theo qui c cch vit cc cht tham d
phn ng dng tn ti thc trong dung dch, v vy khi vit phng trnh cn ch
:
+ Cht in li mnh c vit di dng ion;
+ Cht in li yu v cht bay hi vit di dng phn t;
25
+ Cht rn vit di dng phn t hoc nguyn t.
* Cc bc tin hnh:
- Bc 1: Xc nh dng oxi ho - kh trng thi u v trng thi cui
- Bc 2: Vit cc na phn ng oxi ho - kh
+ Vit cng thc cc dng oxi ho v kh lin hp
+ Cn bng s nguyn t (cn bng khi lng mi nguyn t 2 v)
+ Cn bng in tch (thm bt electron in tch 2 v bng nhau)
+ Bc 3: T hp cc na phn ng thnh phn ng y bng cch nhn
h s thch hp tng electron nhng bng tng electron nhn)
+ Bc 4: iu chnh mi trng nu cn thit
- V d minh ho:
10FeSO
4
+ 2KMnO
4
+ 16KHSO
4
5Fe
2
(SO
4
)
3
+ 2MnSO
4
+ 9K
2
SO
4
+
8H
2
O
5x 2Fe
2+
2Fe
3+

2x MnO
4
-


+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
10FeSO
4
+ 2KMnO
4
+ 16KHSO
4
5Fe
2
(SO
4
)
3
+ 2MnSO
4
+ 9K
2
SO
4
+
8H
2
O
3. Th oxi ho - kh hay th in cc
a. Th in cc (hay th oxi ho - kh)
- Kh nng oxi ho - kh c c trng bng kh nng nhng nhn
electron ca cht khi tham gia phn ng ho hc. c trng cho kh nng ny
ngi ta dng i lng th oxi ho - kh. so snh kh nng phn ng bng cc
i lng o c ngi ta s dng i lng th in cc.
- Th in cc l in th ca mt in cc ang xt. o c th in
cc ngi ta o sc in ng ca pin (E
pin
) to thnh do vic ghp mt in cc
26
so snh (in cc hiro tiu chun c th in cc quy c bng 0,00 V) vi in
cc ang xt.
Qui c: i vi 1 pin, in cc c kh nng cho electron l anot, in cc
nhn electron l catot nn E
pin
= E
c
E
a
(Vi E
c
l E
catot
, E
a
l E
anot
). E
pin
lun
lun l mt i lng dng.
- Trong iu kin chun (hot cc cht u bng n v), th in cc tiu
chun E
0
cng ln th dng oxi ho cng mnh, dng kh cng yu v ngc li.
Phn ng oxi ho - kh t xy ra gia dng oxi ho ca cp c E
0
ln vi dng kh
ca cp c E
0
nh hn..
Qui c v du:
E
0
< 0: dng oxi ho yu hn H
+
, dng kh mnh hn H
2

E
0
> 0: dng oxi ho mnh hn H
+
, dng kh yu hn H
2

b. S ph thuc th theo nng . Phng trnh Nernst.
Xt i vi na phn ng: aOx + ne bKh, th phng trnh Nernst c
dng:
E = E
0
Ox/Kh +
b
a
Kh
O
n ) (
) (
lg
0592 , 0
X
( 25
o
C) (1)
Nu dung dch long coi hot bng nng , ta c:

E = E
0
Ox/Kh +
| |
| |
b
a
X
Kh
O
n
lg
0592 , 0
(2)
Phng trnh 2 l phng trnh hay c s dng nht tnh th oxi ho - kh
4. Hng s cn bng oxi ho - kh. Chiu hng xy ra phn ng oxi ho -
kh
a. Hng s cn bng ca phn ng oxi ho - kh.
- i vi tng phn ng oxi ho - kh thun nghch, 25
o
C ta c:
27
n
2
Ox
1
+ n
1
e Kh
1
K
1
=
0592 , 0 / 1
0
1
10
E n

n
1
Kh
2
Ox
2
+ n
2
e K
2
-1
=
0592 , 0 / 2
0
2
10
E n

n
2
Ox
1
+ n
1
Kh
2
n
2
Kh
1
+ n
1
Ox
2
K = K
1
.K
2
-1
=

0592 , 0 / ) ( 2
0
1
0
2 1
10
E E n n

Trong :
+ E
0
1
, E
0
2
l th oxi ho - kh ca tng cp tng ng.
+ n
1
, n
2
: l s electron tron trao i ca cc qu trnh kh v oxi ho tng
ng.
+ n
1
n
2
l tng s electron tham gia phn ng.
- Bit E
0
ca cc cp oxi ho - kh c th tnh hng s cn bng ca cc na
phn ng tng ng v ngc li:
K =
0592 , 0 / /
0
10
k o nE

E
0
Ox/kh
=
n
K lg 0592 , 0

- tnh E
0
ca mt cp oxi ho - kh bt k, cn thc hin theo cc bc:
+ Vit phng trnh na phn ng ca cp oxi ho - kh nghin cu.
+ T hp cc na phn ng ring l sao cho thu c cn bng ca na phn
ng cn xt
+ Tnh K v t tnh E
0

b. Chiu hng xy ra phn ng oxi ho - kh.
- Da vo hng s cn bng hoc th oxi ho - kh
K > 1: Phn ng xy ra theo chiu thun E
Oxh1/kh1
> E
Oxh2/kh2

K < 1: Phn ng xy ra theo chiu nghch E
Oxh1/kh1
< E
Oxh2/kh2

K = 1: Phn ng trng thi cn bng E
Oxh1/kh1
= E
Oxh2/kh2

28
- Vy phn ng oxi ho - kh din ra theo chiu:
Cht oxi ho mnh + cht kh mnh Cht kh yu hn + cht oxi ho
yu hn.
V c khi qut theo theo qui tc "anpha":
E
Oxh1/kh1
> E
Oxh2/kh2

Chiu phn ng l: Oxh1 + Kh2 Oxh2 + Kh1
- Dy in ho:
+ Dy in ho ca kim loi l mt dy nhng cp oxi ho - kh ca cc
kim loi c sp xp theo chiu tng dn th oxi ho - kh iu kin chun.
Li
+
K
+
Ba
2+
Ca
2+
Na
+
Mg
2+
Al
3+
Mn
2+
Zn
2+
Cr
3+
Fe
2+
Ni
2+
Sn
2+
Pb
2+
Fe
3+
2H
+


Li K Ba Ca Na Mg Al Mn Zn Cr Fe Ni Sn Pb Fe H
2


Cu
2+
Fe
3+
Hg
2
2+
Ag
+
Hg
+
Pt
2+
Au
3+


Cu Fe
2+
2Hg Ag Hg Pt Au
+ Theo dy trn th : Tnh oxi ho tng dn, tnh kh gim dn.
+ ngha ca dy in ho : Cho php d on phn ng xy ra gia hai
cp oxi ho kh theo qui tc
V d : Xt 2 cp Zn
2+
/Zn v Cu
2+
/Cu.
Theo qui tc ta d dng thy phn ng xy ra theo chiu:
Cu
2+
+ Zn Cu + Zn
2+

Oxh
m
+ Kh
m
Kh
y
+ Kh
y

29
5. in phn
* L thuyt v in phn:
- Khi t mt in p vo 2 th in cc nhng vo trong mt dung dch
in li th s xy ra s in phn
Trn catt xy ra qu trnh kh: M
n+
+ ne M
Trn ant xy ra qu trnh oxi ho: X
n-
X + ne
- qu trnh in phn c th xy ra c:
+ in p phi t vo catt: E (-) < E
c
=
| |
| |
+ +
b
a
kh Oxh
Kh
Ox
n
E

lg
0592 , 0
/
0
c

+ in p phi t vo ant: E (+) > E
a
=
| |
| |
+ +
b
a
kh Oxh
Kh
Ox
n
E

lg
0592 , 0
/
0
a

b a
, : qu th trn 2 in cc
Vy in p phi t vo bnh in phn:
E = E (+) E (-) > E
a
E
c
+ IR
I: Cng dng qua bnh in phn
R: in tr bnh in phn
- Th t in phn:
+ Nu trn catt, ant tp trung nhiu cht c kh nng in phn th th t
in phn trn 2 cc l:
Trn catt cht no c E
c
dng hn th in phn trc
Trn ant cht no c E
a
m hn th in phn trc
+ Th t in phn gn ng ca mt s cation, anion thng gp (in cc
tr):
Cation: Ag
+
> Fe
3+
> Cu
2+
> H
+
> Fe
2+
> Zn
2+
>> Al
3+
> Mg
2+
> Na
+
> Ca
2+
> K
+

30
Anion: I
-
> Br
-
> Cl
-
> OH
-
>> NO
3
-
> SO
4
2-
- Qu trnh in phn tun theo nh lut Faraday:
F n
t I A
m
.
. .
=
Trong :
+ m: khi lng cht in phn (g)
+ I: cng dng in phn (A)
+ A: khi lng mol nguyn t, phn t ca cht (g/mol)
+ t: thi gian in phn (s)
+ n: s electron trao i
+ F: hng s Faraday. F = 96500 (C/mol)
III. CC DNG BI TP C BN THNG GP

1 Bi tp cn bng phng trnh phn ng oxi ho - kh

* Nguyn tc:
- Vn dng cc phng php cn bng phng trnh phn ng oxi ho - kh
d on sn phm v cn bng phng trnh.
- Trnh by t hp cc bc, khng cn trnh by r cc bc lm
Bi 1: Vit y v cn bng phng trnh phn ng cho di dng sau:
a) FeSO
4
+ K
2
Cr
2
O
7
+ H
2
SO
4
Fe
2
(SO
4
)
3
+ Cr
2
(SO
4
)
3
+
b) PbO
2
+ Mn
2+
MnO
4
-
+
Li gii:
a) Xc nh cp oxi ho - kh: Trong phn ng trn s oxi ho ca Fe tng
v s oxi ho ca Cr gim. V vy c 2 cp oxi ho - kh l: Fe
3+
/Fe
2+
v Cr
2
O
7
2-
/Cr
3+

Cn bng phng trnh phn ng:
31
6x Fe
2+
Fe
3+
+ 1e
1x Cr
2
O
7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O

6Fe
2+
+ Cr
2
O
7
2-
+ 14H
+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O
Phng trnh phn t:
6FeSO
4
+ K
2
Cr
2
O
7
+ 7H
2
SO
4
3Fe
2
(SO
4
)
3
+ Cr
2
(SO
4
)
3
+ K
2
SO
4
+ 7H
2
O
b) Trong phn ng trn c s thay i s oxi ho ca Mn: tng t +2 ln +7,
chng t y l phn ng oxi ho - kh, trong Mn
2+
ng vai tr cht kh, hnh
thnh nn cp oxi ho - kh th nht l MnO
4
-
/Mn
2+
.
Nh vy PbO
2
s ng vai tr cht oxi ho (vi s oxi ho ca Pb l +4), s
b kh v dng c s oxi ho thp hn (dng kh lin hp), hnh thnh nen cp oxi
ho - kh th hai l PbO
2
/Pb
2+
:
2 Mn
2+
+ 4 H
2
O MnO
4
-
+ 8H
+
+ 5e
qu trnh oxi ho
5 PbO
2
+ 4H
+
+ 2e Pb
2+
+ 2H
2
O qu trnh kh
2Mn
2+
+ 5PbO
2
+ 4H
+
2MnO
4
-
+ 5Pb
2+
+ 2H
2
O
Phng trnh phn t:
2Mn(NO
3
)
2
+ 5PbO
2
+ 4HNO
3
2HMnO
4
+ 5Pb(NO
3
)
2
+ 2H
2
O
Bi 2: ( thi HSGQG nm 2004)
Vit phng trnh ho hc cho mi trng hp sau:
a) Trong mi trng baz, H
2
O
2
oxi ho Mn
2+
thnh MnO
2
.
b) Trong mi trng axit, H
2
O
2
kh MnO
4
-
thnh Mn
2+
.
Li gii:
a) H
2
O
2
+ 2 e 2 OH

S kh
32
Mn
2+
+ 4 OH

2 e MnO
2
+ 2 H
2
O S oxi ho

Mn
2+
+ H
2
O
2
+ 2 OH

MnO
2
+ 2 H
2
O
b) 2 MnO
4

+ 8 H
3
O
+
+ 5 e Mn
2+
+ 12 H
2
O S kh
5 H
2
O
2
+ 2 H
2
O 2 e O
2
+ 2 H
3
O
+
S oxi ho
2MnO
4
-
+ 5 H
2
O
2
+ 6 H
3
O
+
2 Mn
2+
+ 5 O
2
+ 14 H
2
O

2 Bi tp xc nh chiu phn ng gia cc cp oxi ho - kh

* Nguyn tc:
- C hai cp oxi ho - kh Oxh1/kh1 (E
0
1
), Oxh2/kh2 (E
0
2
) vi E
0
1
>E
0
2
th
phn ng xy ra theo chiu:
Oxh1 + kh2 Kh1 + Oxh2
- Xc nh cc yu t nh hng n phn ng:
i vi na phn ng: aOx + ne bKh
Ta c : E
oxh/kh
= E
0
oxh/kh
+
nF
RT
lg
( )
( )
b
a
Kh
Ox

Theo phng trnh Nernst ta thy nhit , s e trao i, nng cc cht c nh
hng n phn ng.
Bi 1: Da vo gi tr th in cc tiu chun, hy xc nh chiu phn ng xy ra
trong cc trng hp sau y:
a) Cr
2
O
7
2-
+ FeCl
2
+ H
+
Cr
3+
+ Fe
3+

b) MnO
4
-
+ Br
-
MnO
2
+ Br
2

c) MnO
2
+ S MnO
4
-
+ S
2-
+ H
2
O
d) MnO
4
-
+ Ag MnO
4
2-
+ Ag
+

Cho bit:
33
2 4
/
0
MnO MnO E
= 1,695 (V) Ag Ag E /
0
+
= 0,799 (V)

2
4 4
/
0
MnO MnO E
= 0,564 (V)
2
/
0
S S E = -0,48 (V)

Br Br E 2 /
0
2
= 1,065 (V)
+ 3 2
7 2
/
0
Cr O Cr E =1,33(V)
+ + 2 3
/
0
Fe Fe E = 0,771(V)
Ligii:
a)
+ 3 2
7 2
/
0
Cr O Cr E >
+ + 2 3
/
0
Fe Fe E do kh nng oxi ho ca Cr
2
O
7
2-
ln hn ca
Fe
3+
nn phn ng xy ra theo chiu thun.
Tng t ta c:
b)
2 4
/
0
MnO MnO E
>

Br Br E 2 /
0
2
nn phn ng xy ra theo chiu thun
c)
2 4
/
0
MnO MnO E
>
2
/
0
S S E nn phn ng xy ra theo chiu nghch
d) 2
4 4
/
0
MnO MnO E
< Ag Ag E /
0
+
nn phn ng xy ra theo chiu nghch
Bi 2 : (Trch thi Olympic Hng Vng nm 2009)
nghin cu cn bng sau 25
o
C
Cu(r) + 2Fe
3+
(dd) Cu
2+
(dd) + Fe
2+
(dd)
Ngi ta nhng mt thanh ng vo mt dung dch hn hp gm CuSO
4

0,5M, FeSO
4
0,025M v Fe
2
(SO
4
)
3
0,125M.
a) Cho bit chiu ca phn ng.
b) Tnh hng s cn bng ca phn ng.
c) T l
] [
] [
2
3
+
+
Fe
Fe
c gi tr nh th no phn ng i chiu.
Bit: V E V E
o
Fe Fe
o
Cu Cu
77 , 0 ; 34 , 0
2 3 2
/ /
= =
+ + +

Li gii :
Ta c [Cu
2+
] = 0,5M, [Fe
2+
] = 0,025M, [Fe
3+
] = 2.0,125 = 0,25M
34

0 ) ( 495 , 0 331 , 0 826 , 0
) ( 331 , 0 5 , 0 lg 34 , 0
) ( 826 , 0 lg 059 , 0 77 , 0
2
059 , 0
/
025 , 0
25 , 0
/
2
2 3
> = =
= + =
= + =
+
+ +
V E
V E
V E
pu
Cu Cu
Fe Fe

=> Phn ng xy ra theo chiu thun
b. Ta c
14
059 , 0
) 34 , 0 77 , 0 ( 2
059 , 0
10 . 77 , 3 576 , 14 lg = = = =

K K
o
pu
nE


c. i chiu phn ng phi c:
8
] [
] [
] [
] [
/ /
10 . 6 , 3 lg 059 , 0 77 , 0 331 , 0 0
2
3
2
3
2 3 2

< + > > <
+
+
+
+
+ + +
Fe
Fe
Fe
Fe
Fe Fe Cu Cu
pu
E E E

3 Bi tp v pin in

* Khi nim pin in
- Pin in cu to gm 2 in cc cng tip xc vi mt dung dch cht in
li ng vai tr l mt ngun in
- Mt in cc xy ra qu trnh oxi ho, gi l ant, nm bn tri, l cc
m (-)
- Mt in cc xy ra qu trnh kh, gi l catt, nm bn phi, l cc
dng (-)
- Sc in ng ca pin: E
pin
= E
c
E
a
( Hoc E
pin
= E
+
- E
-
)
* Nguyn tc:
- Xc nh cp oxi ho - kh trong phn ng
- Xc nh in cc to nn t cp oxi ho - kh
+ in cc loi 1: Thanh kim loi nhng vo dung dch cha ion ca kim
loi . in cc M
n+
/ M.
+ in cc loi 2: Kim loi c ph 1 hp cht t tan ca kim loi
35
V d: in cc Calomen Hg / Hg
2
Cl
2
/ Cl
-

+ in cc kh:
V d: Pt,H
2
/ 2H
+
; Pt,O
2
/ OH
-

+ in cc oxi ho - kh: Mt thanh kim loi tr nhng vo dung dch c
ng thi c hai dng oxi ho v kh ca mt cht
- Cn c vo th oxi ho - kh chun xc nh ant, catt ca pin. T
lp s pin chnh xc
Bi 1:
Thit lp s pin khi pin hot ng th xy ra cc phn ng sau:
a) MnO
4
-
+ Cr
3+
+ H
+
Cr
2
O
7
2-

b) H
2
+ 2Ag
+
2H
+
+ 2Ag
c) Ag
+
+ Br
-
AgBr
Li gii:
a) Trong mi trng axit MnO
4
-
b kh v Mn
2+
, hnh thnh 2 cp oxi ho -
kh:
MnO
4
-
/Mn
2+
v Cr
2
O
7
2-
/Cr
3+

Qu trnh kh MnO
4
-
v Mn
2+
xy ra trn catt:
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
Qu trnh oxi ho Cr
3+
ln Cr
2
O
7
2-
xy ra trn ant:
Cr
3+
+ 7H
2
O Cr
2
O
7
2-
+ 14H
+
+ 6e
Vy ta c s pin :
(a) Pt | Cr
2
O
7
2-
, Cr
3+
, H
+
|| MnO
4
-
, Mn
2+
, H
+
| Pt (c)
b) Trong phn ng trn c hai cp oxi ho - kh l 2H
+
/H
2
v Ag
+
/Ag
Qu trnh kh Ag
+
v Ag xy ra trn catt:
Ag
+
+ 1e Ag
36
Qu trnh oxi ho H
2
thnh 2H
+
xy ra trn ant:
H
2
2H
+
+ 2e
Vy ta c s pin :
(a) Pt, H
2
| 2H
+
|| Ag
+
| Ag (c)
c) Phn ng Ag
+
+ Br
-
AgBr xy ra km theo s thay i nng ca ion
Ag
+
, v vy phi chn in cc lm vic thun nghch vi ion Ag
+
: Ag | Ag
+

v
Ag | AgCl , Cl
-
.
Th ca in cc c tnh theo phng trnh:
| |
+
+ =
+
+
Ag E E Ag Ag
Ag Ag
lg 0592 , 0 /
0
/
. Nh vy in cc no c th ln hn (tc l
c [Ag
+
] ln hn) s l catt. vy ta c s pin:
(a) Ag | AgCl,Cl
-
|| Ag
+
| Ag (c)
catt xy ra qu trnh kh: Ag
+
+ e Ag
ant xy ra qu trnh oxi ho: Ag + Cl
-
AgCl + e

Ag
+
+ Cl
-
AgCl
Bi 2: 25
o
C, sc in ng ca pin:
H
2
(Pt), pH
2
= 1atm | H
+
1M || Hg
2+
1M | Hg bng +0,85 V
Vit phng trnh thc t xy ra trong pin khi pin lm vic v tnh Hg Hg E /
0
2+
.
Li gii:
E
0
pin
> 0 nn E
0
pin
= Hg Hg E /
0
2+
-
2
/ 2
0
H H E
+
= 0,85 V Hg Hg E /
0
2+
Hg Hg E /
0
2+
= 0,85 V
catt (cc thu ngn) xy ra qu trnh kh:
Hg
2+
+ 2e Hg
37
ant (cc hiro) xy ra qu trnh oxi ho:
H
2
2H
+
+ 2e
Vy phn ng thc t xy ra khi pin lm vic nh sau:
Hg
2+
+ H
2
Hg + 2H
+

4.Bi tp v cc yu t nh hng n sc in ng ca pin

*Nguyn tc:
- Cc yu t nh hng n phn ng oxi ho - kh v sc in ng ca pin
chnh l cc yu t nh hng n sc in ng ca pin.
Theo phng trnh Nernst: E
pin
= E
c
E
a
= E
0
+
| || |
| || | 1 xh2
2 xh1
lg
Kh O
Kh O
nF
RT

Ta thy, cc yu t nh hng n sc in ng ca pin gm: nhit , s
electron trao i, nng cc cht tham gia phn ng.
Nu mt phn ng nht nh, nhit c nh th nng cht oxi ho,
cht kh c nh hng trc tip n sc in ng ca pin (hay th oxi ho - kh)
Bi 1:
Cho pin: (-) Pt, Fe
3+
(0,100M), Fe
2+
(0,05M), H
+
(1M) || HCl (0,02M) | AgCl |
Ag (+)
Xt nh hng nh tnh ti sc in ng ca pin nu:
a. Thm 50 ml HClO
4
vo na tri ca pin
b. Thm mui Fe
2+
vo na tri ca pin
c. Thm KMnO
4
vo na tri ca pin
d. Thm NaOH vo na tri ca pin
e. Thm t NaCl tinh th vo na phi ca pin
f. Thm 10 ml nc vo na phi ca pin
Li gii:
Xt pin in trn khi pin hot ng:
38
1 Fe
2+
Fe
3+
+ e
1 AgCl + e Ag
+
+ Cl
-


Fe
2+
+ AgCl Fe
3+
+ Ag
+
+ Cl
-

Catt (+) E
c
= Ag Ag E /
0
+
+ 0,0592lg[Ag
+
]
M [Ag
+
] =
| |

Cl
K
S

| |

+ =
+
Cl
K
E E
S
Ag Ag
c
lg 0592 , 0 /
0

Ant (-):
| |
| |
+
+
+ =
+ +
2
3
/
0
lg 0592 , 0
2 3
Fe
Fe
E E Fe Fe
a

Sc in ng ca pin:

| |
| || |
+
+
+ = =
+ + +
Cl Fe
Fe
E E E E E Fe Fe Ag Ag
a c pin 3
2
/
0
/
0
lg 0592 , 0
2 #

Vy sc in ng ca pin ph thuc vo: [Fe
3+
], [Fe
2+
] v [Cl
-
]
a)V sc in ng ca pin khng ph thuc vo nng ion H
+
nn khi thm
H
+
vo na tri ca pin th E
pin
khng i
* Lu : gim pH dung dch khng lm thay i E
pin
nhng nu tng pH s to
phc hiroxo v c th to kt ta ion kim loi, khi s nh hng n E
pin
.
a) Thm mui Fe
2+
vo na tri ca pin lm tng nng ion Fe
2+
, d E
pin

cng tng.
b) Thm KMnO
4
vo na tri ca pin s xy ra phn ng oxi ho - kh sau:
MnO
4
-
+ 5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
Nng Fe
2+
gim xung, cn nng Fe
3+
tng ln, do E
pin
gim.
c) Thm NaOH vo na phi ca pin s xy ra phn ng:
Ag
+
+ OH
-
AgOH
Nng Ag
+
gim xung, E
c
gim E
pin
gim.
39
d) Thm NaCl vo na phi ca pin [Cl
-
] tng ln E
pin
gim.
e) Thm H
2
O vo na phi ca pin in li ca AgCl tng, lm tng nng
ca Cl
-
E
pin
gim
Bi 2: Ngi ta thc hin mt pin gm:
(-) Zn|Zn(NO
3
)
2
0,1M || AgNO
3
0,1M | Ag (+)
Mi na pin gm100 ml dung dch.
Cho ) ( 799 , 0 /
0
V E Ag Ag =
+
; ) ( 76 , 0 /
0
2
V E Zn Zn =
+

a) Vit phng trnh phn ng khi pin lm vic v tnh E
pin

b) Tnh E
pin
khi:
- Thm vo 2 na pin 0,01 mol NaOH
- Thm vo 2 na pin 1 mol NH
3
(gi s Vdd khng i)
Li gii:
a) Khi pin lm vic:
Zn Zn
2+
+ 2e
Ag
+
+ e Ag

Zn + 2Ag
+
Zn
2+
+ 2Ag
Ta c : E
c
= | |
+
+
+
Ag E Ag Ag lg 059 , 0 /
0

E
a
= | |
+
+
+
2
/
0
lg
2
059 , 0
Zn E Ag Ag
E
pin
= E
c
E
a
= 1,52 (V)
b) - Thm vo 2 na pin 0,01 mol NaOH, s c kt ta AgOH, Zn(OH)
2

AgOH Ag
+

+ OH
-
K
s
= 10
-7,7

40
Zn(OH)
2
Zn
2+
+ 2OH
-
K
s
= 10
-16,7


Tng t tnh li nng cc ion trong dung dch: [Ag
+
] = 10
-3,85
, [Zn
2+
] = 0,05
Thay cc gi tr trn vo biu thc tnh E
pin
= 1,37 (V)
- Thm vo 2 na pin 0,1 mol NH
3
,
3
NH
C = 1M s c phn ng to phc amin
c 2 in cc
Ag
+
+ 2NH
3
Ag(NH
3
)
2
+
; = 10
7,23
Zn
2+

+ 4NH
3
Zn(NH
3
)
4
2+
; = 10
8,70

Tnh li nng ca mi cation trong dung dch hai in cc:
[Ag
+
] = 9,2.10
-9
M; [Zn
2+
] = 1,53.10
-9
M
) ( 345 , 1 V E
pin
=
*Nhn xt: Qua bi tp trn ta thy vic tnh li sc in ng ca pin khi c
thm cc yu t khc (cht kt ta, cht to phc, pha long dung dch, cht oxi
ho - kh...) thc cht l da theo cc cn bng mi ny tnh li nng cc
cht ri th vo biu thc tnh sc in ng tm gi tr sc in ng mi ca
pin.
5. Bi tp in phn dung dch cht in li

Bi 1: in phn 100 ml dung dch AgNO
3
0,01M trong mi trng HClO
4
1M
bng in cc platin. Cng dng in phn l 1,5A, in tr dy dn l 100
m, qu th ca hiro, oxi trn in cc platin l: -3,0 V v 0,53 V
a) Tm in p t vo 2 in cc Ag
+
bt u in phn
b) Tm in p t vo 2 in cc bt u c kh hiro thot ra catt.
Khi lng bc cn li l bao nhiu?
c) Tm thi gian in phn hon ton Ag
+
, th tch kh oxi (ktc) thu c
trong thi gian in phn trn?
Hng dn:
41
- u tin vit cc qu trnh phn li trong nc ca cc cht, cc phn ng xy
ra ti cc in cc: cation in phn ti catt, anion in phn ti ant.
- Tnh th ti catt ca cc cht (ch qu th) v xc nh th t in phn.
Trong bi ny:
Ti catt:
Ag
+
in phn trc, H
+
in phn sau
Ag
+
in phn hon ton khi [Ag
+
] = 10
-6
M
Ti ant:
H
2
O b in phn gii phng oxi
- in p t vo 2 in cc c qu trnh in phn l:
E = E
c
E
a
+ I.R
- Khi lng cht thu c tnh theo nh lut Faraday
Li gii:
Phn ng in phn:
AgNO
3
Ag
+
+ NO
3
-

HClO
4
H
+
+ ClO
4
-


Catt (-) Ant (+)
Ag
+
, H
+
, H2O
Ag
+
+ e Ag
2H
+
+ 2e H2
H2O, NO3
-
, ClO4
-

2H2O 4H
+
+ 4e + O2


- Th trn catt ca ion Ag
+
: E
c
= Ag Ag E /
0
+
+ 0,0592lg[Ag
+
]
42
Th Ag
+
bt u in phn: E
c1
= 0,799 + 0,0592lg0,01 = 0,6806 (V)
Th Ag
+
in phn hon ton : E
c2
= 0,799 + 0,0592lg10
-6
= 0,4438 (V)
- Th trn catt ca ion hiro:
E
c
= 0,0592lg[H
+
] + H
2
= -0,3 (V)
So snh E
c
ta thy Ag
+
s in phn hon ton trc khi hiro b in phn
- Th trn ant:
| |
+ + =
+
2
2 2
4
/
0
lg
4
0592 , 0
O
O H O
a
P
H
E E O
2
= 1,23 + 0 + 0,53 = 1,76 (V)
a) Th in p Ag
+
bt u in phn:
E
1
= E
a
E
c1
+ I.R = 1,76 + 0,6806 + 1,5.1 = 1,228 (V)
b) Khi H
+

bt u in phn th th t vo bnh l:
E
2
= 1,76 (- 0,3) + 0,15 = 2,21 (V)
c) Thi gian in phn hon ton Ag
+
: ( ) ( 08 , 1 108 . 01 , 0 g m
Ag
= =
+

=
F n
t I A
m
.
. .
I A
F n m
t
.
. .
= =
. 5 , 1 . 108
96500 . 1 . 08 , 1
=643,33 (s)
Trong thi gian , th tch oxi thu c ktc l:
) ( 056 , 0 0025 , 0 .
4
1
2 2
l V mol n n
O
Ag
O
= = =
+
Bi 2: Mt dung dch cha ng thi Cu(NO
3
)
2
0,1M v Cd(NO
3
)
2
0,1M. in
phn dung dch ny bng bnh in phn c in cc platin, qu th ca kim loi
trn platin bng 0.
a) C th tch hon ton Cu
2+
ra khi dung dch khng?
b) Kim loi no s tch ra trc khi thm KCN vo dung dch trn v gi
nng KCN khng i l 0,4M
Cho bit: ) ( 337 , 0 /
0
2
V E Cu Cu =
+
; ) ( 402 , 0 /
0
_ 2
V E Cd Cd =
Li gii:
43
a)
- Th trn catt ca ion Cu
2+
: E
c
= | |
+
+
+
2
/
0
lg
2
0592 , 0
2
Cu E Cu Cu
Th Cu
2+
bt u in phn: E
c1
= 0,337 +
2
0592 , 0
lg0,1 = 0,3074 (V)
Th Cu
2+
in phn hon ton : E
c2
= 0,337 +
2
0592 , 0
lg10
-6
= 0,1594 (V)
- Th trn catt ca ion Cd
2+
:
E
c
= -0,402 + 1 , 0 lg
2
0592 , 0
= 0,4316 (V)
So snh E
c
ta thy Cu
2+
s in phn hon ton trc khi Cd
2+
b in phn.
V vy c th tch hon ton Cu
2+
ra khi dung dch
b) Khi thm KCN vo dung dch trn, xy ra phn ng sau:
Cu
2+
+ 2CN
-
Cu(CN)
2

2
= 10
25

Cd
2+
+ CN
-
[Cd(CN)]
+

1
= 10
6,01

Cd
2+
+ CN
-
[Cd(CN)
2
]
2
= 10
11,12

Cd
2+
+ CN
-
[Cd(CN)
3
]
-

2
= 10
15,65

Cd
2+
+ CN
-
[Cd(CN)
2
]
2-

2
= 10
17,92
6. Bi tp v hng s cn bng ca phn ng oxi ho - kh:
* Nguyn tc: T E
0
ca cc cp oxi ho - kh c th tnh hng s cn bng ca
cc na phn ng tng ng v ngc li da vo biu thc sau:
K =
0592 , 0 / /
0
10
k o nE

E
0
Ox/kh
=
n
K lg 0592 , 0


44
Bi 1: Tnh hng s cn bng i vi phn ng sau:
2AgCl + Cu Ag + Cu
2+
+ 2Cl
-

Cho Ag Ag E /
0
+
= 0,80 (V); ) ( 337 , 0 /
0
2
V E Cu Cu =
+
;
( )
10
10

=
AgCl S
K
Li gii:
2 AgCl + e Ag + Cl
-
K
1
=
( ) 0592 , 0 / /
0
10
Ag AgCl E

1 Cu Cu
2+
+ 2e K
2
-1
=
( ) 0592 , 0 / 2 /
2
0
10
Cu Cu E
+



2AgCl + Cu 2Ag + Cu
2+
+ 2Cl
-

0592 , 0 / . 2 1
2
2
1
0
10 .
E
K K K

= =
Trong =
0
E Ag AgCl E /
0
Cu Cu E /
0
2+
v Ag AgCl E /
0
c tnh t s t hp ca cn bng
sau:
AgCl Ag
+
+ Cl
-
K
S(AgCl)
= 10
-10

Ag
+
+ e Ag K
3
=
0592 , 0 / ) ( /
0
10
Ag Ag E
+


AgCl + e Ag + Cl
-
K
1
= K
3
.K
S(AgCl/Ag)
= 10
-10
.
0592 , 0 / ) ( /
0
10
Ag Ag E
+

0592 , 0 . 10 /
0
/
0
=
+
Ag Ag Ag AgCl E E =0,207 (V)
Vy K =
0592 , 0 / ) 337 , 0 207 , 0 .( 2
10

= 10
-4,39

7. Bi tp tnh cn bng trong dung dch

* Nguyn tc:
tnh cn bng oxi ho - kh khi trong dung dch khng c cc qu trnh
ph th c th tnh thnh phn da vo nh lut tc dng khi lng p dng cho
cn bng oxi ho - kh
45
Nu hng s cn bng qu ln th nn xc nh thnh phn gii hn v tnh
theo cn bng ngc li.
Nu c cc qu trnh ph km theo cn bng oxi ho - kh th nn tm cch
nh gi mc ca cc cn bng ph so vi cn bng oxi ho - kh hoc tnh
theo hng s cn bang iu kin
Trong trng hp phc tp khi h c cha cn bng c lin quan n phn
ng axit baz th c th tnh theo iu kin proton.
Bi 1 : Tnh cn bng trong dung dch AgNO
3
0,02M v Fe(NO
3
)
2
0,050M pH =
0.
Cho : ); ( 799 , 0 /
0
V E Ag Ag =
+
) ( 771 , 0
2 3
/
0
V E Fe Fe =
+ +

Li gii : Trong mi trng H
+
, b qua qu trnh to phc hiroxo ca ion kim loi
Cn bng ch yu:
Ag
+
+ Fe
2+
Ag + Fe
3+
K =
473 , 0 0592 , 0
771 , 0 799 , 0
10 10 =


C 0,02 0,05
[] (0,02-x) (0,05-x) x

473 , 0
10
) 05 , 0 )( 02 , 0 (
=
x x
x

| |
4 3
10 . 58 , 4
+
= = Fe x ; [Fe
2+
] = 0,0495M; [Ag
+
] = 0,0195 M.
Bi 2: Tnh hng s cn bng ca phn ng
3MnO
4
2-
+ 2H
2
O 2MnO
4
-
+ MnO
2
+ 4OH
-
Cho: ) ( 695 , 1
2 4
/ ,
0
V E MnO H MnO =
+
;
2
4 4
/
0
MnO MnO E =0,564 (V).
Tnh cn bng trong dung dch K
2
MnO
4
pH = 10,00.
Li gii:
Tnh
2
2
4
/
0
MnO MnO E

= ?
46
MnO
4
2-
MnO
4
-
+ e
0592 , 0 / 1
1
0
1
10
E
K

=

MnO
4
2-
+ 4H
+
+3e MnO
2
+ 2H
2
O
0592 , 0 / . 3
2
0
2
10
E
K =
4.| H
2
O H
+
+ OH
-

4 14 2
W
) 10 (

= K

MnO
4
2-
+ 2H
2
O + 2e MnO
2
+ 4OH
-
K
3
=
0592 , 0 / . 2
0
3
10
E


) ( 603 , 0 0592 , 0 . 28
2
564 , 0 695 , 1 . 3
2
0592 , 0 . 4 . 14
2
3
0
1
0
2
0
3
V
E E
E =

=
Vy
2
2
4
/
0
MnO MnO E

= 0,603 (V)
MnO
4
2-
+ 2H
2
O + 2e MnO
2
+ 4OH
-

2. | MnO
4
2-
MnO
4
-
+ e

3MnO
4
2-
+ 2H
2
O 2MnO
4
-
+ MnO
2
+ 4OH
-
K = 20,08
pH = 10,00 th:
| |
| |
15
4 4 3
2
4
2
4
10 . 078 , 2
) 10 (
78 , 20
= =

MnO
MnO
rt ln, c th coi phn ng xy ra
hon ton.

IV. MT S BI TP TNG HP

Bi 1( thi chn hc sinh gii quc gia nm 2005)
pH = 0 v 25
o
C th in cc tiu chun E
o
ca mt s cp oxi ho - kh
c cho nh sau:
2IO
4

/ I
2
(r) 1,31 V ; 2IO
3

/ I
2
(r) 1,19 V ; 2HIO/ I
2
(r) 1,45 V ; I
2
(r)/ 2I

0,54
V.
47
(r) ch cht trng thi rn.
1. Vit phng trnh na phn ng oxi ho - kh ca cc cp cho.
2. Tnh E
o
ca cc cp IO
4

/ IO
3

v IO
3

/ HIO
3. V phng din nhit ng hc th cc dng oxi ho - kh no l bn, cc dng
no l khng bn? Ti sao?
4. Thm 0,40 mol KI vo 1 lt dung dch KMnO
4
0,24 M pH = 0
a) Tnh thnh phn ca hn hp sau phn ng.
b) Tnh th ca in cc platin nhng trong hn hp thu c so vi in
cc calomen bo ho.
5. Tnh E
o
ca cp IO
3

/ I
2
(H
2
O).
I
2
(H
2
O) ch it tan trong nc.
Cho bit:
+ 2 2
4
/
0
Mn MnO E = 1,51 V ; E ca in cc calomen bo ho bng 0,244 V ;
25
o
C, ln = 0,0592 lg ; tan ca it trong nc bng 5,0.10
4
M.
Li gii:
2 IO
4

+ 16 H
+
+ 14 e I
2
(r) + 8 H
2
O ;
2 4
/ 2
0
I IO E

= 1,31(V) = E
0


2 IO
3

+ 12 H
+
+ 10 e I
2
(r) + 6 H
2
O ;
2 3
/ 2
0
I IO E


= 1,19 V = E
o
2
2 HIO + 2 H
+
+ 2 e I2(r) + 2 H2O ;
2
/ 2
0
I HIO E

= 1,45 V = E
o

I2 (r) + 2 e 2 I

I I E 2 /
0
2

= 0,54 V = E
o
4
RT
F
48
2.
2 IO
4

+ 16 H
+
+ 14 e I
2
(r) + 8 H
2
O ; K
1

=
0592 , 0 / 14 1
0
10
E

I
2
(r) + 6 H
2
O 2 IO
3

+ 12 H
+
+ 10 e ; K
2
-1
=
0592 , 0 / 10 2
0
10
E


2 IO
4

+ 4 H
+
+ 4 e 2 IO
3

+ 2 H
2
O ; K
5

=
5
0
4
10
E


Vi E
0
5
=

3 4
/
0
IO IO E
K
5
= K
1
. K
2
1
=
0592 , 0 / 14 1
0
10
E
.
0592 , 0 / 10 2
0
10
E
=
5
0
4
10
E


4
10 14 2
0
1
0
5
0
E E
E

= =
4
19 , 1 . 10 31 , 1 . 14
= 1,61 (V)
2 IO
3

+ 12 H
+
+ 10 e I
2
(r) + 6 H
2
O ; K
2

=
0592 , 0 / 10 2
0
10
E


I
2
(r) + 2 H
2
O 2 HIO + 2 H
+
+ 2 e ; K
3
1
=
0592 , 0 / 2 3
0
10
E

2 IO
3

+ 10 H
+
+ 8 e 2 HIO + 4 H
2
O ; K
6
=

6
0
8
10
E


Vi K
6
=
HIO IO
K
/
3

=K
2
.K
3
-1
=

=
8
2 10 3
0
2
0
6
0
E E
E
8
45 , 1 . 2 19 , 1 . 10
=1,125 (V)



3. V
2
/ 2
0
I HIO E > HIO IO E /
0
3


nn HIO s t oxi ho - kh:
4 2 HIO + 2 H
+
+ 2 e I
2
(r) + 2 H
2
O
2 HIO + 4 H
2
O 2 IO
3

+ 10 H
+
+ 8 e

10 HIO 4 I
2
(r) + 2 IO
3

+ 2 H
+
+ 4 H
2
O
Vy dng km bn nht v mt nhit ng hc l HIO, cc dng khc: IO
4
-
, IO
3
-
, I
2
,
I
-
u bn pH = 0.
4. a)
+ 2 2
4
/
0
Mn MnO E

= 1,51 V >>

I I E 2 /
0
2
(

I I E 2 /
0
2
nh nht) nn u tin s xy ra
phn ng:
49
2 MnO
4

+ 8 H
+
+ 5 e Mn
2+
+ 4 H
2
O
5 2 I


I
2
(r) + 2 e

2 MnO
4

+ 10 I

+ 16 H
+
2 Mn
2+
+ 5 I
2
(r) + 8 H
2
O ; K =

10
163

C
O
0,24 0,4
C 0,04 2 0,04 10 0,04 2 0,04 5
C 0,16 0 1 0,08 0, 2
MnO
4

cn d s oxi ho tip I
2
thnh IO
3

.


+ 2 2
4
/
0
Mn MnO E

= 1,51 V >
2 3
/ 2
0
I IO E

= 1,19 V
2 x MnO
4

+ 8 H
+
+ 5 e Mn
2+
+ 4 H
2
O
I
2
(r) + 6 H
2
O 2 IO
3

+ 12 H
+
+ 10 e

2 MnO
4

+ I
2
(r) + 4 H
+
2 IO
3

+ 2 Mn
2+
+ 2 H
2
O ; K =

10
176

C
O
0,16 0,2 0,08
C 0,08 2 0,08 0,08 2 0,08 2
C 0 0,12 1 0,16 0, 24
Thnh phn hn hp sau phn ng: IO
3

0,16 M ; Mn
2+
0,24 M ;
I
2
(H
2
O) 5. 10
4
M ; I
2
(r) 0,12 M ; pH = 0.
b) Trong hn hp c cp IO
3

/ I
2
(r) nn:
E =
2 3
/ 2
0
I IO E

+
10
0592 , 0
lg [IO
3

]
2
[H
+
]
12


= 1,19 +
10
0592 , 0
lg (0,16)
2
= 1,18 V
50
E so vi in cc calomen bo ho: 1,18 0,244 = 0,936 V
5. 2 IO
3

+ 12 H
+
+ 10 e I
2
(r) + 6 H
2
O ; K
2

= 10
10.1,19/ 0,0592

I
2
(r) I
2
( H
2
O) ; S = 5. 10
4
M

2 IO
3

+ 12 H
+
+ 10 e I
2
( H
2
O) + 6 H
2
O ; K
7

= 10
10
= 10
10.1,19/
0,0592
. S
Suy ra E
o
7
=
2 3
/ 2
0
I IO E

+ lg S .
10
0592 , 0

= 1,19 + (lg 5. 10
4
) .
10
0592 , 0
= 1,17 V
Bi 2: ( thi hc sinh gii quc gia nm 2004)
Dung dch A gm AgNO
3
0,050 M v Pb(NO
3
)
2
0,100 M.
1. Tnh pH ca dung dch A.
2. Thm 10,00 ml KI 0,250 M v HNO
3
0,200 M vo 10,00 ml dung dch A.
Sau phn ng ngi ta nhng mt in cc Ag vo dung dch B va thu c v
ghp thnh pin (c cu mui tip xc hai dung dch) vi mt in cc c Ag nhng
vo dung dch X gm AgNO
3
0,010 M v KSCN 0,040 M.
a) Vit s pin .
b) Tnh sc in ng E
pin
ti 25
0
C .
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng .
Cho bit : Ag
+
+ H
2
O AgOH + H
+
(1) ; K
1
= 10
11,70

Pb
2+
+ H
2
O PbOH
+
+ H
+
(2) ; K
2
= 10
7,80

Ch s tch s tan pK
s
: AgI l 16,0 ; PbI
2
l 7,86 ; AgSCN l 12,0 .

;
RT
ln = 0,0592 lg
F
= 0 ,799 V
E
0
Ag
+
/Ag

3. E
pin
s thay i ra sao nu:
a) thm mt lng nh NaOH vo dung dch B ;
51
b) thm mt lng nh Fe(NO
3
)
3
vo dung dch X?
Li gii:
1. Ag
+
+ H
2
O AgOH + H
+
; K
1
= 10
-11,7

(1)
Pb
2+
+ H
2
O PbOH
+
+ H
+
; K
2
= 10
-7,8

(2)
Do K
2
>> K
1
nn cn bng 2 quyt nh pH ca dung dch
Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8

(2)
C 0,10
| | 0,10 x x x
8 , 7
2
10
x 1 , 0
x

=

x = 10
-4,4
= |H
+
| ; pH = 4,40
2.a) Dung dch B: Thm KI : C
Ag+
= 0,025 M; C
Pb2+
= 0,050
C
I
- = 0,125M ; C
H+
= 0,10M
Ag
+
+ I

AgI
0,025 0,125
- 0,10
Pb
2+
+ 2 I

PbI
2

0,05 0,10
- -
Trong dung dch c ng thi hai kt ta AgI v PbI
2

AgI Ag
+
+ I

; K
s1
= 1.10
-16
(3)
PbI
2
Pb
2+
+ 2 I

; K
s2
= 1.10
-7,86
(4)
K
s1
<< K
s2
, vy trong dung dch cn bng (4) l ch yu. S
52
to phc hiroxo ca Pb
2+
l khng ng k v c H
+
d:
Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8


| |
| |
| | | |
+ +

+
+
<< = =
2 8 , 6
1
8 , 7
2
Pb PbOH 10
10
10
Pb
PbOH

Trong dung dch PbI
2
Pb
2+
+ 2 I

K
s2
= 1.10
-7,86

x 2 x
(2x)
2
x = 10
-7,86
x = 1,51.10
-3
M 2x = [I

] = 2,302 . 10-
3
M
| |
| |
M 10 . 31 , 3
10 . 02 , 3
10 . 1
I
K
Ag
14
3
16
1 s

+
= = =
.
E ca cc Ag trong dung dch A: Ag+ + e Ag
| |
V 001 , 0 E
10 . 31 , 3 lg 0592 , 0 799 , 0 Ag lg 0592 , 0 E E
1
14 0
Ag
Ag
1
=
+ = + =
+
+

Dung dch X: Ag+ + SCN AgSCN ; 10
12,0
0,010 0,040
- 0,030 0,010
AgSCN Ag+ + SCN ; 10
-12,0
0,030
x (0,030 + x)
x0,030 + x) = 10-12
| |
11
2
12
10 . 33 , 3
10 x 3
10
x Ag

+
= = =

| |
V 179 , 0 E
10 . 33 , 3 lg 0592 , 0 799 , 0 Ag lg 0,0592 0,799 E
2
11
2
=
+ = + =
+

53
V E2 > E1 , ta c pin gm cc Ag trong X l cc + , cc Ag trong B
l cc
S pin:
AgI AgSCN
PbI2 SCN 0,03 M

b) Epin = 0,179 0,001 = 0,178V
c) Phng trnh phn ng: Ag + I AgI + e
AgSCN + e Ag + SCN

AgSCN + I Ag + SCN

d) K =
AgI
AgCN
S
S
K
K
=
16
12
10
10

= 10
4


3. a) Khi thm lng nh NaOH vo dung dch B , c th xy ra 3 trng
hp:
- Lng NaOH qu t khng trung ho HNO3: S to phc
hiroxo ca Pb2+ vn khng ng k, do Epin khng thay i.
- Lng NaOH trung ho HNO3: C s to phc hiroxo ca
Pb2+ do |Pb2+| gim, Nng I - s tng ln, do nng Ag+ gim
xung, E1 gim ; vy Epin tng.
- Lng NaOH d trung ho ht HNO
3
v ho tan PbI
2
to
Ag Ag
54
thnh PbO
2
-
, do |Pb2+| gim v Epin tng.
PbI
2
+ 4 OH
-
PbO
2
+ 2 H
2
O + 2 I

c) Thm t Fe
3+
vo dung dch X:
Fe
3+
+ SCN

FeSCN
2+

Nng ion SCN

gim, do nng ion Ag


+
tng, E
2
tng
E
pin
tng
Bi 3 ( thi chn hc sinh gii quc gia nm 2006)
Hy biu din s pin gm in cc hiro (p = 1atm) c nhng trong
dung dch CH
3
COOH 0,010 M ghp (qua cu mui) vi in cc Pb nhng trong
dung dch A. Hy ch r anot, catot.
b) Thm 0,0050 mol Ba(OH)
2
vo 1 lt dung dch pha in cc hiro (coi th
tch khng thay i). Tnh E
pin
v vit phng trnh phn ng xy ra khi pin hot
ng.
Cho: pK
a
(HSO
4
-
) 2,00 ; pK
a
(CH
3
COOH) 4,76;
ch s tch s tan pK
s
(BaSO
4
) 9,93 ; pK
s
(PbSO
4
) 7,66.
(RT/F)ln = 0,0592lg ; E
o
= - 0,123 V.
Li gii:
2. a) Cc Hiro: 2 H
+
+ 2e H
2

CH
3
COOH H
+
+ CH
3
COO

; K
a
= 10
-4,76

C 0,01
[ ] 0,01 - x x x
= 10
-4,76
x = [H
+
] = 4,08.10
-4
M pH = 3,39
2
/ 2 H H
E
+
= - 0,0592 pH = - 0,0592 3,39 = - 0,2006 (V)
H2

Pb
2+
/P
b
55
Cc Pb/PbSO
4
:
PbSO
4
+ H
+
+ 2 e Pb + HSO
4


E
Pb
=
+
4 4
, / ,
0
HSO Pb H PbSO E

+
2
0592 , 0
lg
| |
| |

+
4
HSO
H


Trong

+
4 4
, / ,
0
HSO Pb H PbSO E = Pb Pb E /
0
2+
+
2
0592 , 0
lg
a
S
K
K
= - 0,291

E
Pb
= - 0,291 +
2
0592 , 0
lg
0943 , 0
1657 , 0
= - 0,283 (V) <
2
/ 2 H H
E
+


(Hoc: E = Pb PbSO E /
0
4
+
| |
2
4
1
lg
2
0592 , 0
SO


M Pb PbSO E /
0
4

= Pb Pb E /
0
2+

+
2
0592 , 0
lg K
S

= - 0,123 +
2
0592 , 0
lg10
-7,66
= - 0,350 (V)

Vy E = - 0,350 +
2
0592 , 0
lg(5,69.10
-3
)
-1
= - 0,284 (V) ;
Cng c th tnh theo cp Pb
2+
/Pb:
E = - 0,123 +
2
0592 , 0
lg [Pb
2+
] = -0,123 +
2
0592 , 0
lg 3,84.10
-6
= - 0,283 (V)
Vy cc Pb l anot; cc hiro l catot.
56
( ) (anot) Pb PbSO
4
, H
+
CH
3
COOH H
2
(Pt) (+) (catot)
BaSO
4
, HSO
4
-
b) 2 CH
3
COOH + Ba(OH)
2
(CH
3
COO)
2
Ba + 2 H
2
O
0,010 0,005
----- ----- 0,005
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-
; K
b
= 10
-9,24

C 0,010
[ ] 0,010 - x x x
= 10
-9,24
x = 10
-5,62
pH = 8,38
E = - 0,0592 pH = - 0,0592.8,38 = - 0,496 V (anot)
E = - 0,284 V (catot)
Vy E
pin
= - 0,284 - (- 0,496) = 0,212 V.
Phn ng trong pin: anot H
2
2 H
+
+ 2e
2 CH
3
COO
-
+ 2 H
+
2 CH
3
COOH

2 CH
3
COO
-
+ H
2
2 CH
3
COOH + 2e
catot PbSO
4
+ H
+
+ 2 e Pb + HSO
4


Phn ng xy ra trong pin:
PbSO
4
+ H
2
+ 2 CH
3
COO
-
+ H
+
Pb + 2 CH
3
COOH + HSO
4



VI. BI TP VN DNG
Bi 1: Hon thnh cc phng trnh ho hc sau:
2H
+
/H
2

PbSO
4
/Pb
x
2

0,010 - x
57
a) SnS
2
+ .... H
2
SnO
3
+ SO
4
2-
+ NO
2

b) PbO
2
+ H
2
O
2
+ ... Pb(CH
3
COO)
2

c) Pt + HCl + ... NO + H
2
O
d) AuCl
4
-
+ ... Fe
3+
+ Cl
-
+ Au
Bi 2: Da vo gi tr th in cc tiu chun, hy cho bit nhng trng hp no
phn ng xy ra theo chiu thun?
a) HClO + H
2
O
2
HCl + O
2
+ H
2
O
b) Cr
2
O
7
2-
+ I
-
+ H
+
Cr
3+
+ I
2
+ H
2
O
c) H
3
AsO
4
+ I
2
+ H
+
H
3
AsO
3
+ I
-
+ H
2
O
d) CrO
2-
+ OH
-
+ Cl
-
Cl
2
+ CrO
4
2-
+ H
2
O

Bi 3: Cho s pin:
(a) H
2
(Pt), atm p
H
1
2
= |H
+
1M || Cu
2+
1M, I
-
1M, CuI| Pt (c)
E
pin
= 0,86 V.
Tnh th in cc tiu chun ca cp Cu
2+
/Cu. Cho bit phn ng xy ra khi pin
hot ng?
Bi 4: Tnh th ca in cc platin nhng trong dung dch:
a) Cr
2
O
7
2-
0,010M; Cr
3+
0,1M pH = 2,00
b) Dung dch bo ho Fe(OH)
3
, Fe(OH)
2
pH = 10,00. Cho
V E OH Fe OH Fe 52 , 0
2 3
) ( / ) (
0
=
Bi 5: Cho pin c ghp bi 2 cc Ag | AgCl | HCl 0,02 M v Pt | Fe
3+
0,10 M;
Fe
2+
0,05M; H
+
1 M. Vit s pin. Xt nh hng (nh tnh) ti s ca pin,
nu:
a) Thm 50 ml HClO
4
1 M vo dung dch catt
b) Thm nhiu mui Fe
3+
vo dung dch catt
c) Thm t NaOH vo dung dch ant
d) Thm 10 ml nc vo dung dch catt
58
Bi 6: Tnh sc in ng ca pin c to thnh bi in cc platin nhng trong
dung dch Ce
3+
0,05M, Ce
4+
0,10M, H
2
SO
4
1,0M v in cc calomen bo ho
Vit cc phng trnh phn ng thc t xy ra khi pin hot ng v vit s pin.
Cho V E
Calomen
244 , 0 =
Bi 7: Tnh hng s cn bng i vi phn ng sau:
a) 2Fe
2+
+ I
3-
3I
-
+ 2Fe
3+
( V E E I I Fe Fe 5355 , 0 ; 771 , 0 /
0
/
0
3 2 3
= =
+ +
)
b) 2Hg + 2Hg
2+
2Hg
2
2+
( V E V E Hg Hg Hg Hg 792 , 0 ; 907 , 0 /
0
/
0
2
2
2
2
2
= =
+ + +
)
c) 5PbO
2
+ 2Mn
2+
+ 4H
+
2MnO
4
-
+ 5Pb
2+
+ 2H
2
O
( V E V E Mn MnO Pb PbO 51 , 1 ; 455 , 1
2
4
2
2
/
0
/
0
= =
+ +
)
Bi 8: Tnh hng s cn bng ca cc phn ng sau 25
o
C:
a) CrO
2
-
+ MnO
4
-
+ H
2
O CrO
4
2-
+ MnO(OH)
2

b) 2CrO
4
2-
+ 4H
2
O 2CrO
2
-
+ 3H
2
O
2
+ 2OH
-

Bi 9: Lc mt t bt Ag vi dung dch Fe
3+
0,01M v H
+
1M. Tnh nng cc
ion Ag
+
v Fe
2+
khi cn bng c thit lp?
Bi 10: Trn 25 ml K
2
Cr
2
O
7
0,08M vi 15 ml KBr 0,08M pH = 0. Tnh th in
cc platin nhng trong dung dch thu c so vi in cc Ag | AgCl | HCl 1M (E
0

= 0,222V)








59
Chuyn 3
PIN IN HA
Trng THPT Chuyn Nguyn Tt Thnh, Yn Bi

CHNG I: C S L THUYT
I. MT S KHI NIM CHNH YU V PIN IN HA
1. Khi qut chung. Nng lng gi mt vai tr c bit quan trng trong i
sng x hi v trong sn xut ni chung. Nng lng ho hc l mt trong cc
dng nng lng c sinh ra t cc phn ng ho hc. Dng nng lng ny c
th chuyn ho thnh cc dng nng lng khc v ngc li. Trong chuyn ny
chng ti ch cp n dng nng lng xut pht t phn ng oxi ho - kh.
2. Phn ng oxi ho - kh
2.1 Mt s nh ngha
Mt cch c th, ta xt phn ng gia Zn v Cu
2+
trong dung dch nc:


Zn
nhng e
Cht kh
Qu trnh oxi ho
+ Cu
2+

nhn e
Cht oxi ho
Qu trnh kh

Zn
2+
+ Cu
Trong phn ng ny c s chuyn e t Zn sang Cu
2+

Qu trnh oxi ho: qu trnh nhng e (Zn Zn
2+
+ 2e)
Qu trnh kh: qu trnh nhn e (Cu
2+
+2e
-
Cu)
Cht oxi ho (cht b kh): cht nhn e, (Cu
2+
)
Cht kh (cht b oxi ho): cht nhng e, (Zn)
Hai qu trnh ny lun lun xy ra ng thi trong cng mt phn ng nn
phn ng loi ny c gi l phn ng oxi ho - kh.
2e


60
2.2. Cp oxi ho - kh (Ox/Kh)
Phn ng oxi ho - kh ni trn c th c biu din theo s sau:


Zn + Cu
2+


Zn
2+
+ Cu

Hoc vit thnh hai na phn ng:
Zn
Cu
2+


+
Zn
2+

2e
-

+

2e
-

Cu

Kh
1

Ox
2


+
Ox
1

ne
-

+

ne
-

Kh
2

(1)
(2)

Zn + Cu
2+


Zn
2+
+ Cu Kh
1
+ Ox
2


Ox
1
+ Kh
2

Theo nh ngha, chng ta c th biu din qu trnh trn bng s sau:
Ox + ne
-
Kh
Trong na phn ng (1), Zn nhng e, gi vai tr ca tc nhn kh (Kh
1
);
Zn
2+
c kh nng nhn e (trong phn ng nghch) gi vai tr ca tc nhn oxi ha
(Ox
1
). Ta c cp oxi ho - kh: Ox
1
/Kh
1
(Zn
2+
/Zn).
Mt cch tng t, trong na phn ng (2) ta c cp oxi ho - kh:
Ox
2
/Kh
2
(Cu
2+
/Cu).
Nh vy, trong mt phn ng oxi ho - kh c s trao i e gia tc nhn kh
Kh
1
(Zn) ca mt cp oxi ho - kh v tc nhn oxi ho Ox
2
(Cu
2+
) ca mt cp oxi
ho - kh khc (tng t nh phn ng axit - baz v cp axit - baz trong thuyt
axit baz ca Bronsted).

3. Pin Ganvani
3.1. Nguyn tc hot ng ca pin Ganvani
Pin Ganvani (gi tt l pin) l thit b cho php chuyn ho nng lng ho
hc thnh nng lng in (xem s pin).
Xt phn ng gia Zn v dung dch Cu
2+
c ni trn:

2e


61

Zn + Cu
2+


Zn
2+
+ Cu
Phn ng ny c th d dng quan st trc tip
bng mt.
Nhng mt thanh km (Zn) vo dung dch
CuSO
4
, sau mt thi gian ngn ta thy ngay c s
hnh thnh mt lp ng ph trn thanh km.
Trong trng hp ny, electron chuyn trc
tip t Zn sang Cu
2+
.
Nh bit, phn ng trn l phn ng trc
tip tng hp ca 2 na phn ng. Cc phn ng
xy ra in cc:
Zn 2e Zn
2+
Cu
2+
+ 2e Cu
Chng ta c th tch ring hai na phn ng
trn bng cch ngn cn khng cho e chuyn trc tip t Zn sang Cu
2+
m qua dy
dn. Cc na phn ng by gi xy ra trn cc thanh km v ng, cc thanh ny
c gi l cc in cc.
Phn ng oxi ho: Zn Zn
2+
+ 2e
-
xy ra trn in cc km. in cc ny
gi l anot. Trong na phn ng ny, cc e c gii phng chuyn vn qua dy
n thanh ng to nn dng in (lu rng, chiu quy c ca dng in l
chiu ngc li).
Phn ng kh: Cu
2+
+ 2e Cu xy ra trn in cc ng gi l catot.
Nh rng: phn ng oxi ho lun lun xy ra trn anot cn phn ng kh lun
lun xy ra trn catot. Tt c cc pin Ganvani u hot ng theo mt c ch tng
t. Pin Ganvani ni trn, vi hai in cc km - ng c tn l pin Daniell - Jacobi,
thng gi tt l pin Daniell.
Pin Daniell c biu din bng
s quy c sau y:
() Zn, Zn
2+
,, Cu
2+
, Cu (+)
i vi pin (ngun in) th anot
l cc m () v catot l cc dng
(+).
Trong pin in ha, cc electron
chuyn t anot sang catot nh dy





SO
Zn
2+
Zn
Cu
2-
4
2+
Cu
CuSO
4
ZnSO
4

S pin Ganvani
-
-
-
-
dd CuSO
4
dd KCl bo ho
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
--
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
- - -
-
-
-
-
-
-
-
-
-
-
-
-
- -
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
- - - -
dd ZnSO
4
Zn
- - - -
- - - -
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Cu
+
62
dn in, cn chiu dng in c
quy c ngc vi dng electron.




Pin Daniell - Jacobi
II. MT S IN CC
1. in cc kim loi
in cc kim loi gm mt thanh kim loi nhng trong dung dch mui ca
n.
Gia kim loi v dung dch xut hin mt s hiu in th. Gi tr ca hiu s in
th ny ph thuc vo bn cht kim loi, bn cht dung mi, nng ion kim loi
trong dung dch v nhit . Gi tr ny khng xc nh c nn phi ly mt in
cc lm chun v gn cho n mt gi tr th in cc so snh vi cc in cc
khc. in cc c chn l in cc chun hiro.
in cc kim loi v in cc hiro gi l cc in cc loi mt.
2. in cc chun hiro
V khng xc nh c gi tr tuyt i ca
in th mt in cc, ngi ta phi chn mt in
cc no lm chun so snh v cho n mt gi
tr in th nht nh. in cc chun so snh c
quc t chp nhn l in cc hiro chun.
in cc hiro l mt in cc kh thuc loi
in cc oxi ho - kh. in cc gm mt tm Pt
ph mui platin v nhng vo mt dung dch axit,
cha ion H
+
, Vy in cc ny lm vic vi cp oxi
ha kh H
+
/H
2
. Th ca in cc chun hiro c
quy c bng 0,00V mi nhit .
2H
+
.aq + 2e

H
2
(k) E
2
0
/ H H
+
= 0,00V


2
H
+
H + HSO
2
H
Pt
4


63
Gi tr ny c gi l th in cc chun hiro
hoc th kh chun ca hiro hoc th oxi ha
kh chun hiro.

in cc hiro
in cc chun l in cc m tt c cc phn ng xy ra trn in cc u
iu kin chun (trng thi bn nht, p = 1 atm, C = 1M).
3. in cc calomen
in cc calomen l in cc lm vic vi cp oxi ha kh Hg
2
Cl
2
/Hg
Hg
2
Cl
2(tt)
+ 2e

2Hg (l) + 2Cl


-

E
0
= + 0,268 V
in cc calomen l in cc loi hai.
Hai in cc loi hai khc cng hay c dng l in cc bc clorua v
in cc thy ngn (I) sunfat:
AgCl(tt) + e

Ag (tt) + Cl
-

E
0
= + 0,222V
Hg
2
SO
4
(tt) + 2e

2Hg (l) + SO
2
4

E
0
= + 0,615V
4. in cc gm kim loi tr nhng vo dung dch cha mt cp oxi ha kh
Kim loi tr thng dng cho loi in cc ny l platin. V d, kim loi
platin nhng trong dung dch cha cp oxi ha kh Fe
3+
/ Fe
2+
.
Cc in cc kiu ny l in cc loi ba.
Th ca in cc loi ba ph thuc vo bn cht kim loi lm in cc, bn
cht ca cp oxi ha kh, t l nng gia dng oxi ha v dng kh v vo
nhit .
5. iu kin chun ca cc loi in cc
Mt in cc iu kin chun khi nng ca mi cu t tham gia phn
ng in cc bng 1,0 mol/L. Nu l cht kh th p sut ring phn ca mi cu t
tham gia phn ng in cc l 1,0 atm. Nu l cht rn th phi dng tinh th
nguyn cht di p sut 1,0 atm. Nu l cht lng th phi l nguyn cht di
p sut 1,0 atm.
64
6. Th in cc chun
c th so snh c th in cc ca cc loi in cc khc nhau, ngoi
vic quy nh iu kin chun ca cc loi in cc, cn phi quy c chiu ca
phn ng in cc v nhit . Ngi ta quy c chiu ca cc phn ng in cc
l chiu ca qu trnh kh:
Ox + ne

kh hocvit ngc li: kh

ox + ne
th du ca th in cc phi i (gi tr tuyt i bng nhau).
Chnh da vo d quy c ny m th in cc cng c tn l th kh. Tuy
nhin, cng c mt s ti liu c vit l th oxi ha kh.
V th in cc ph thuc vo nhit nn s so snh th in cc ca cc
in cc khc nhau phi cng nhit .
7. Xc nh th in cc chun
xc nh th in cc
chun ca mt in cc no
, ngi ta thit lp mt pin
gm in cc chun cn xc
nh th v in cc chun
hiro, ri o hiu s in th
ln nht gia hai in
cc.Hiu s in th ln nht
o c l th in cc
chun ca in cc cn xc
nh, v th cc chun hiro

Zn
1M
Zn
2+
-
H
1M
4
SO
2-
H
+
H
2
2
1atm
- +
+


c quy c bng 0,00 V. Th in cc chun xc nh c k hiu l E
0

(ox/kh).

Th in cc chun xc nh c s c gi tr dng, nu in cc cn o th in
cc dng (catot) ca pin so vi in cc chun hiro. Ngc li nu in cc cn
65
xc nh th l in cc m (anot) so vi in chun hiro, th gi tr o c s c
du m. V d:
(-) Pt H
2
(1,0atm), H
+
.aq (1,0M) Cu
2+
.
aq(1,0M) Cu (+); E
0

(Cu2+/Cu)
= + 0,337
V
(-) Pt H
2
(1,0atm), H
+
.aq (1,0M) Zn
2+
.aq (1,0M) Zn (-); E
0

(Zn2+/Zn)
= - 0,736 V
Trong thc t ngi ta thng dng mt in cc so snh khc in cc loi hai,
chng hn in cc calomen. Th in cc chun ca in cc calomen 25
0
C l
E
0
(Hg
2
Cl
2
/Hg) = + 0,268 V. in cc calomen dng trong dung dch bo ha KCl
c E (Hg
2
Cl
2
/Hg) = + 0,24 V. Gi tr th kh chun ca mt cp oxi ha kh cng
ln (tr s i s) th dng oxi ha (ox) c tnh oxi ha cng mnh v dng kh (kh)
th tnh kh cng yu v ngc li.
III. Phng trnh Nernst:
Xt phn ng: a ox + ne

b kh
Phng trnh Nernst c dng:
E(ox/kh) = E
0
(ox/kh) +
[ox]
ln
[ ]
a
b
RT
nF kh

R: l hng s kh l tng, R = 8,314 J.K
-1
.mol
-1
.
F: l hng s Faraday, F = 96,5 .10
3
C.mol
-1
.
T : Nhit tuyt i, T = t + 273 (K).
n:l s electron trao i gia hai dng ox v kh.
a v b l cc h s t lng ng trc cc dng ox v kh.
25
0
C, phng trnh Nernst c dng:
E(ox/kh) = E
0
(ox/kh) +
[ox]
log
[ ]
a
b
kh


Sc in ng ca ca phn ng oxi ho - kh biu din qua nng :
Kh
1
+ Ox
2
Ox
1
+ Kh
2

66
= +
o 2 1
1 2
[Ox ][Kh ] RT
E E ln
nF [Ox ][Kh ]

Tng qut cho mt phn ng biu din qua nng di dng:
aA bB + cC dD +
Ta c th vit: = +
a b
o
c d
RT [A] [B]
E E ln
nF
[C] [D]

Trong phng trnh ny mun c s chnh xc th nng phi c thay bng
hot .
Khi chuyn v dng logarit thp phn ta c:
= +
a b
o
c d
0,59 [A] [B]
E E log
n
[C] [D]

V d: Cu
2+


+ 2e

Cu
E (Cu
2+
/Cu) = E
0
(Cu
2+
/Cu) +
2
0, 059
g[ ]
2
lo Cu
+

Cu th rn, c coi l hng s:
2H
+
+ 2e

H
2
(k)
E(H
+
/H
2
) = E
0
(H
+
/H
2
) +
2
2
0, 059 [ ]
l g
2
H
H
o
p
+

i vi cht kh, dng p sut (atm) thay cho nng mol/L
-1
.
MnO
4

+ 5e + 8H
+

Mn
2+
+ 4H
2
O (l)
E(MnO
4

/Mn
2+
) = E
0
(MnO
4

/Mn
2+
) +
8
4
2
[ ][H ] 0, 059
log
5 [ ]
MnO
Mn
+
+

IV. Sc in ng ca pin
Sc in ng ca pin l hiu in th gia hai u ca pin:
( ) ( ) pin
E E E
+
=
E
+
: th kh ca in cc dng (V).
67
E
-
: th kh ca in cc m (V).
Nu pin c cu to bi hai in cc chun th:
E
0
pin
=
0 0
E E
+

V. Chiu phn ng oxi ha kh trong dung dch:
Theo nhit ng hc quan h gia
G
va
E
s l:

G nF E =
Trong : n l s electron trao i gia cht oxi ha v cht kh trong phn ng;
F = 96,5.10
3
C.mol
-1
.
E = E (ox1/kh1) E (ox2/kh2) . Trong E (ox1/kh1) v E (ox2/kh2)
l th kh ca cc cp oxi ha kh theo phng trnh:
ox1 + kh2

ox2 + kh1
Khi: G < 0, phn ng xy ra theo chiu thun;
G > 0. Phn ng xy ra theo chiu nghch;
G = 0 , phn ng trng thi cn bng.
Khi phn ng iu kin chun (nng cc cu t trong dung dch tham
gia phn ng, k c sn phm bng 1,0 mol/L; nu l cht kh th p sut ring
phn l 1,0 atm; th chiu phn ng c xc nh bng biu thc sau:
0 0 0 0
ox1/ 1 ox2/ 2
( )
kh kh
G nF E nF E E = =
VI. Quan h gia sc in ng ca pin v hng s cn bng K ca phn ng
oxi ho - kh xy ra trong pin
Phn ng oxi ho - kh xy ra trong pin Ganvani lm xut hin mt dng
in. Trong qu trnh phng in, nng ca cc cht phn ng gim v nng
ca cc sn phm tng. Khi phn ng t ti trng thi cn bng th sc in ng
ca pin bng khng. Theo phng trnh Nernst: Xt phn ng tng qut:
aA bB + cC dD +
68
Hng s cn bng l: =
c d
a b
[C] [D]
K
[A] [B]

Phng trnh Nernst c dng: = +
a b
o
c d
0,59 [A] [B]
E E log
n
[C] [D]

hoc vit: =
c d
o
a b
0,059 [C] [D]
E E log
n
[A] [B]
thay gi tr K ta c:
=
o
0,059
E E logK
n

trng thi cn bng E = 0 (K l hng s cn bng) ta s c:
=
o
0,059
E logK 0
n

hay =
o
nE
logK
0,059

H thc ny cho php ta xc nh hng s cn bng K ca phn ng t gi tr
E
o
.


CHNG II: BI TP
A. BI TP mu
Bi 1:
1. Cho cc th in cc ca cc cp oxi ha kh sau:
NO
3
-
/ NO
2
-
c E
0
1
= 0,94 V NO
2
-
/NO c E
0
2
= 1,00 V
NO
3
-
/N
2
c E
0
3
= 1,22 V N
2
/NH
4
+
c E
0
4
= 0,27 V
Tnh th tiu chun E
0
ti pH = 0 ca mi cp oxi ha kh sau:
NO
3
-
/NO v NO
3
-
/NH
4
+

2. Cho pin sau c E
0
= 0,11V:
(-)Ag ddAg
2
SO
4
bo ha AgNO
3
2M Ag (+)
69
a. Vit phng trnh phn ng xy ra trn mi in cc v trong pin
b. Tnh tan ca Ag
2
SO
4
trong nc nguyn cht 25
0
C
bit cp Ag
+
/Ag c E
0
= 0,8 V.
Bi 2: Phn ng gia AgNO
3
vi KCl trong dung dch to thnh kt ta AgCl v
gii phng nng lng. Ta c th to ra mt t bo in ho (pin) sinh cng in
nh phn ng .
a) Vit cng thc ca t bo in ho theo quy tc IUPAC v cc na phn ng
in cc ti anot v catot.
b) Tnh
0
298
G ca phn ng kt ta AgCl v E
0
298
ca t bo in ho.
Cho: T
AgCl
25
0
C bng 1,6. 10
10
.
Bi 3: Dung dch A gm AgNO
3
0,050 M v Pb(NO
3
)
2
0,100 M.
1. Tnh pH ca dung dch A.
2. Thm 10,00 ml KI 0,250 M v HNO
3
0,200 M vo 10,00 ml dung dch A.
Sau phn ng ngi ta nhng mt in cc Ag vo dung dch B va thu c v
ghp thnh pin (c cu mui tip xc hai dung dch) vi mt in cc c Ag nhng
vo dung dch X gm AgNO
3
0,010 M v KSCN 0,040 M.
a) Vit s pin .
b) Tnh sc in ng E
pin
ti 25
0
C .
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng .
Cho bit : Ag
+
+ H
2
O AgOH + H
+
(1) ; K
1
= 10
11,70

Pb
2+
+ H
2
O PbOH
+
+ H
+
(2) ; K
2
= 10
7,80

Ch s tch s tan pK
s
: AgI l 16,0 ; PbI
2
l 7,86 ; AgSCN l 12,0 .

;
RT
ln = 0,0592 lg
F
= 0 ,799 V
E
0
Ag
+
/Ag

3. E
pin
s thay i ra sao nu: a) thm mt lng nh NaOH vo dung dch B
; b) thm mt lng nh Fe(NO
3
)
3
vo dung dch X?
70
Bi 4:
Bit th oxi ho-kh tiu chun:
E
o
Cu
2+
/Cu
+
= +0,16 V E
o
Fe
3+
/Fe
2+
= +0,77 V
E
o
Cu
+
/Cu = +0,52 V E
o
Fe
2+
/Fe = -0,44 V
Hy cho bit hin tng g xy ra trong cc trng hp sau:
a) Cho bt st vo dung dch Fe
2
(SO
4
)
3
0,5M.
b) Cho bt ng vo dung dch CuSO
4
1M.
Bi 5: Xt kh nng phn ng ca Cl
-
, Br
-
vi KMnO
4
.Bit V E
Br Br
085 , 1
0
2 /
2
=

;
V E
Cl Cl
359 , 1
0
2 /
2
=

; V E
Mn MnO
51 , 1
0
/
2
4
=
+
.
a. pH=0
b. Trong dung dch axit axetic 1,00 M. Bit CH
3
COOH c K
a
=10
-4,76
.
Bi 6: nghin cu cn bng sau 25
o
C
Cu(r) + 2Fe
3+
(dd) Cu
2+
(dd) + Fe
2+
(dd)
Ngi ta cho Cu vo mt dung dch gm CuSO
4
0,5M ; FeSO
4
0,025M ; Fe
2
(SO
4
)
3

0,125M
a. Cho bit chiu ca phn ng.
b. Tnh hng s cn bng ca phn ng
c. T l
] [
] [
2
3
+
+
Fe
Fe
c gi tr nh th no phn ng i chiu
Bit: V E V E
o
Fe Fe
o
Cu Cu
77 , 0 ; 34 , 0
2 3 2
/ /
= =
+ + +

Bi 7: Th ca bn phn ng Fe
2+
Fe
3+
+ e ( E
0
= 0,771 V 298K)
Khi pH ca mi trng thay i th tr s trn thay i th no? (Xc nh c th
trong iu kin nhit bng 25
0
C, nng cc cht pH = 0 u bng n v).
Cho bit: T
t
(Fe(OH)
3
)= 3,8. 10
-38
v T
t
(Fe(OH)
2
)= 4,8. 10
-15
Bi 8: Cho gin th kh chun ca Mn trong mi trng axit:
71
MnO
-
4
MnO
2-
4
MnO
2
Mn
3+
Mn
2+
+0,56V
? ?
+1,51V
+1,7V
+1,23V

Tnh th kh chun ca cc cp MnO
2
4

/MnO
2
v MnO
2
/Mn
3+

Bi 9: Tnh tch s tan ca AgCl 25
0
C bit:
0
Ag / Ag
E 0, 8V
+
= v
0
AgCl / Ag
E 0, 22V = .
Bi 10: nghin cu cn bng sau 25
o
C:
3 2 2
Cu 2Fe Cu 2Fe
+ + +
+ + , ngi ta
trn ba dung dch sau vi th tch bng nhau: Cu(NO
3
)
2
0,3M v Fe(NO
3
)
2
0,06M,
Fe(NO
3
)
3
0,03M. Xc nh chiu v sut in ng ca phn ng trn. Bit rng,
2 3+ 2
o o
Cu / Cu Fe / Fe
E 0, 34V; E 0, 77V
+ +
= = v 25
o
C biu thc xc nh th in cc:
o
OXH/KH OXH/KH
0, 059 [OXH]
OXH + ne KH E E lg
n [KH]
= +

Bi 11:
Cho cn bng sau:
Cu + Cu
2+
+ 2Cl
-

2CuCl
Bit E
0
/
2
Cu Cu
+
= 0,15V; E
0
/ Cu Cu
+
= 0,52 V; K
s
(CuCl) = 10
-7
; nng ban u ca Cu
2+

bng 0,1 M; Cl
-
bng 0,2M; c Cu v CuCl u c th d.
a. Phn ng trn xy ra theo chiu no?
b. Tnh hng s cn bng ca phn ng xy ra v nng mol/l cc ion Cu
2+
;
Cl
-
khi cn bng.
Bi 12: Ngi ta lp mt pin gm hai na pin sau: Zn/Zn(NO
3
)
2
0,1M v
Ag/AgNO
3
0,1M c th kh chun tng ng l V 76 , 0 E
o
Zn / Zn
2
=
+
v
V 80 , 0 E
o
Ag / Ag
+ =
+
.
(a) Thit lp s pin.
(b) Vit phng trnh phn ng khi pin lm vic.
(c) Tnh sut in ng ca pin.
(d) Tnh nng cc ion trong dung dch khi pin ngng hot ng.

72

p n:

Bi 1:
*Ta c NO
3
-
+ 2H
+
+ 2e NO
2
-
+ H
2
O G
0
1
= -2FE
1
0

NO
2
-
+ 2H
+
+ 1e NO + H
2
O G
0
2
= -FE
2
0

NO
3
-
+ 4H
+
+ 3e NO+ H
2
O G
0
5
= -FE
5
0
Suy ra: G
5
0
= G
0
1
+G
0
2
do

2E
1
0
+ E
2
0
2. 0,94 + 1
E
5
0
= = = 0,96 V
3 3
* Ta c NO
3
-
+ 6H
+
+ 5e 1/2 N
2
+3 H
2
O G
0
3
= -5FE
3
0

1/2N
2

+ 4H
+
+ 3e NH
4
+
G
0
4
= -3FE
4
0

NO
3
-
+ 10H
+
+ 8e NH
4
+
+ 3H
2
O G
0
6
= -FE
6
0
Suy ra G
6
0
= G
0
3
+ G
0
4
do 5.1,22 + 3.0,27
5E
3
0
+ 3E
4
0
5.1,22+ 3.0,27
E
6
0
= = = 0,86375V
8 8

- Phn ng trn ant(cc -) : Ag -1e Ag
+

73
- Phn ng trn catt(cc +) : Ag
+
+1e Ag
-Phn ng trong pin: Ag(cc m) + Ag
+
( cc dng) Ag
+
+ Ag
Ta c:
E
0
(-)
= E
0
+ 0,059 lg[ Ag
+
]
(-)
E
0
(+)
= E
0
+ 0,059 lg[ Ag
+
]
(+)
= E
0
+ 0,059 lg2

M E
0
pin
= E
0
(+)
- E
0
(-)
= 0,059lg 2/[ Ag
+
]
(-)
= 0,11V
Suy ra [ Ag
+
]
(-)
= 0,02732 M
Mt khc gi s l tan ca Ag
2
SO
4
trong iu kin cho
Ag
2
SO
4

2Ag
+
+ SO
4
2-


Do 2s = 0,02732 nn s = 1,366. 10
-2

Vy tan ca Ag
2
SO
4
l 1,366. 10
-2
.

Bi 2: a) Na phn ng oxi ho anot: Ag e + Cl

AgCl
Na phn ng kh catot: Ag
+
+ e Ag .
Ag
+
+ Cl

AgCl (r)
Cng thc ca t bo in ho:
(Anot) Ag | dd KCl || dd AgNO
3
| Ag (Catot)
b) Tnh
0
298
G v E
0
298
:
Xt phn ng Ag

+ Cl

AgCl (r)
Kc =
AgCl
1
T
=
10
1
1, 6.10

= 6,25.10
9

74

0
298
G = RTlnKc = 8,314 298 ln (6,25.10
9
) = 55884 J/mol = 55,884
kJ/mol
E
0
298
=
0
G
nF

= +
55884
1 96487
= + 0,5792 (V) + 0,58 V
Bi 3:
1. Ag
+
+ H
2
O AgOH + H
+
; K
1
= 10
-11,7

(1)
Pb
2+
+ H
2
O PbOH
+
+ H
+
; K
2
= 10
-7,8

(2)
Do K
2
>> K
1
nn cn bng 2 quyt nh pH ca dung dch
Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8

(2)
C 0,10
| | 0,10 x x x
8 , 7
2
10
x 1 , 0
x

=

x = 10
-4,4
= |H
+
| ; pH = 4,40
2.a) Dung dch B: Thm KI : C
Ag+
= 0,025 M; C
Pb2+
= 0,050
C
I
- = 0,125M ; C
H+
= 0,10M
Ag
+
+ I

AgI
0,025 0,125
- 0,10
Pb
2+
+ 2 I

PbI
2

0,05 0,10
- -
Trong dung dch c ng thi hai kt ta AgI v PbI
2

75
AgI Ag
+
+ I

; K
s1
= 1.10
-16
(3)
PbI
2
Pb
2+
+ 2 I

; K
s2
= 1.10
-7,86
(4)
K
s1
<< K
s2
, vy trong dung dch cn bng (4) l ch yu. S to
phc hiroxo ca Pb
2+
l khng ng k v c H
+
d:

Pb
2+
+ H
2
O PbOH + H
+
; K
2
= 10
-7,8


| |
| |
| | | |
+ +

+
+
<< = =
2 8 , 6
1
8 , 7
2
Pb PbOH 10
10
10
Pb
PbOH

Trong dung dch PbI
2
Pb
2+
+ 2 I

K
s2
= 1.10
-7,86

x 2 x
(2x)
2
x = 10
-7,86
x = 1,51.10
-3
M 2x = [I

] = 2,302 . 10-
3
M
| |
| |
M 10 . 31 , 3
10 . 02 , 3
10 . 1
I
K
Ag
14
3
16
1 s

+
= = = .
E ca cc Ag trong dung dch A: Ag
+
+ e Ag
| |
V 001 , 0 E
10 . 31 , 3 lg 0592 , 0 799 , 0 Ag lg 0592 , 0 E E
1
14 0
Ag
Ag
1
=
+ = + =
+
+

Dung dch X: Ag
+
+ SCN

AgSCN ; 10
12,0

0,010 0,040
- 0,030 0,010
AgSCN Ag
+
+ SCN

; 10
-12,0

0,030
x (0,030 + x)
76
x0,030 + x) = 10
-12

| |
11
2
12
10 . 33 , 3
10 x 3
10
x Ag

+
= = =
| |
V 179 , 0 E
10 . 33 , 3 lg 0592 , 0 799 , 0 Ag lg 0,0592 0,799 E
2
11
2
=
+ = + =
+

V E
2
> E
1
, ta c pin gm cc Ag trong X l cc + , cc Ag trong B l cc

S pin:
AgI AgSCN
PbI
2
SCN

0,03 M
b) E
pin
= 0,179 0,001 = 0,178V
c) Phng trnh phn ng: Ag + I

AgI + e
AgSCN + e Ag + SCN


AgSCN + I

Ag + SCN



d) K = = = 10
4


3. a) Khi thm lng nh NaOH vo dung dch B , c th xy ra 3 trng hp:

- Lng NaOH qu t khng trung ho HNO
3
: S to phc hiroxo ca
Pb
2+
vn khng ng k, do E
pin
khng thay i.
- Lng NaOH trung ho HNO
3
: C s to phc hiroxo ca Pb
2+
do
|Pb
2+
| gim, Nng I
-
s tng ln, do nng Ag
+
gim xung, E
1
gim ;
Ag Ag
KsAgSCN
Ks
10
12

10
16

77
vy E
pin
tng.
- Lng NaOH d trung ho ht HNO
3
v ho tan PbI
2
to thnh PbO
2

,
do |Pb
2+
| gim v E
pin
tng.
PbI
2
+ 4 OH

PbO
2

+ 2 H
2
O + 2 I



b) Thm t Fe
3+
vo dung dch X:
Fe
3+
+ SCN

FeSCN
2+

Nng ion SCN

gim, do nng ion Ag


+
tng, E
2
tng E
pin
tng

Bi 4: 1. a) E
o
Fe
3+
/Fe
2+
= +0,77 V > E
o
Fe
2+
/Fe = -0,44 V nn:
Tnh oxi ho: Fe
3+
mnh hn Fe
2+

Tnh kh: Fe mnh hn Fe
2+

Do phn ng t pht xy ra gia 2 cp l: 2 Fe
3+
+ Fe 3 Fe
2+

Nh vy Fe tan trong dung dch Fe(SO
4
)
3
to thnh mui FeSO
4
, lm nht mu
vng
( hoc nu) ca ion Fe
3+
v cui cng lm mt mu (hoc to mu xanh nht)
dung dch.
b) E
o
Cu
+
/Cu = + 0,52 V > E
o
Cu
2+
/Cu
+
= + 0,16 V nn:
Tnh oxi ho: Cu
+
mnh hn Cu
2+
Tnh kh: Cu
+
mnh hn Cu
Do phn ng t pht xy ra gia 2 cp l: Cu
+
+ Cu
+
Cu
2+
+ Cu
Phn ng nghch(Cu
2+
phn ng vi Cu to thnh ion Cu
+
) khng xy ra. Do khi
b bt ng vo dung dch CuSO
4
khng xy ra phn ng v quan st khng thy
hin tng g.
Bi 5:
Cc cp oxi ho- kh:
78
Br
2
+ 2e 2Br
-
V E
Br Br
085 , 1
0
2 /
2
=

(1)
Cl
2
+ 2e 2Cl
-
V E
Cl Cl
359 , 1
0
2 /
2
=

(2)
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O V E
Mn MnO
51 , 1
0
/
2
4
=
+
(3)
T (1) v (2) ta thy th ca cc cp khng ph thuc vo pH( trong mi trng
axit), tuy vy th ca cp MnO
4
-
/Mn
2+
li ph thuc pH:
| |
| |
| |
8
2
4 0
. lg .
5
0592 , 0
+
+

+ = H
Mn
MnO
E E | |
| |
| |
+

+
+ + =
2
4
8
0
lg .
5
0592 , 0
lg .
5
0592 , 0
Mn
MnO
H E E

| |
| |
+

+ =
2
4 0
lg 0118 , 0 095 , 0
Mn
MnO
pH E E (4)
a) pH = 0
iu kin tiu chun
0
2 /
0
2 /
0
2 2
51 , 1

> > = =
Br Br Cl Cl
E E V E E . V vy trc ht MnO
4
-

oxi ho Br
-
thnh Br
2
v sau Cl
-
thnh Cl
2
.
b) Trong dung dch CH
3
COOH 1,00M
CH
3
COOH H
+
+ CH
3
COO
-
K
a
= 10
-4,76

C 1,00
[ ] 1,00-x x x
[H
+
] = x =
a
K = 10
-2,38
pH = 2,38
T (4) rt ra: E = E
0
- 0,095pH = 1,51- 0,095.2,38 = 1,28V
Bi v
0
2 /
0
2 /
2 2

< <
Cl Cl Br Br
E E E , nn trong dung dch CH
3
COOH 1M, MnO
4
-
ch oxi
ho c Br
-
thnh Br
2
m khng oxi ho c Cl
-
thnh Cl
2
.
79
Bi 6:
a. Ta c [Cu
2+
] = 0,5M
[Fe
2+
] = 0,025M
[Fe
3+
] = 2.0,125 = 0,25M

0 ) ( 495 , 0 331 , 0 826 , 0
) ( 331 , 0 5 , 0 lg 34 , 0
) ( 826 , 0 lg 059 , 0 77 , 0
2
059 , 0
/
025 , 0
25 , 0
/
2
2 3
> = =
= + =
= + =
+
+ +
V E
V E
V E
pu
Cu Cu
Fe Fe

=> Phn ng xy ra theo chiu thun
b. Ta c
14
059 , 0
) 34 , 0 77 , 0 ( 2
059 , 0
10 . 77 , 3 576 , 14 lg = = = =

K K
o
pu
nE

Bi 7:
Phng trnh ca th oxiho ca qu trnh Fe
2+
Fe
3+
+ e
c dng E = E
0
0,059lg
| |
| |
+
+
2
3
Fe
Fe
(1)
Theo u bi Fe(OH)
3
s bt u kt ta khi:
pH =
3
1
lg
3
) (OH Fe
T lg
O H
K
2
=
3
1
lg 3,8.10
-38
lg10
-14
= 1,52
v Fe(OH)
2
bt u kt ta khi:
pH =
2
1
lg
2
) (OH Fe
T lg
O H
K
2
=
2
1
lg 4,8.10
-15
lg 10
-14
= 6,34
Nh th trong khong pH t 0 1,52 th ca phn ng khng ph thuc vo pH.
Trong khong pH t 1,52 6,34 nng ca Fe
3+
s ph thuc vo pH ca mi
trng.
80
Biu th |Fe
3+
| qua
3
) (OH Fe
T v |OH
-
| qua
O H
K
2
ri thay vo pt(1) ta c:
E = 0,771 0,059lg
| |
3
38
10 . 8 , 3

OH
+ 0,059lg |Fe
3+
|
= 0,771 0,059lg3,8.10
-38
+3.lg|OH
-
| ( |Fe
3+
| =1th lg|Fe
3+
| =0 )
= 0,771 0,059lg3,8.10
-38
+ 3. 0,059lg10
-14
3. 0,059lg|H
+
|
Vi pH = lg |H
+
| ta c E = 1,049 + 0,177pH
T pH = 6,34 tr i c Fe(OH)
2
cng kt ta cng vi Fe(OH)
3
nn phng trnh
(1) c dng:
E = E
0
0,059lg
| |
| |
3
) (
2
) (
.
.
2
3

OH T
OH T
OH Fe
OH Fe

= 0,771 0,059lg 7,91.10
-23
+ 0,059lg10
-14
0,059lg|H
+
|
E = 0,293 + 0,059pH
Bi 8:
* i vi cp MnO
2
4

/MnO
2
ta c:
MnO
4

+ e MnO
2
4

(1) E
0
1
= 0,56 V
MnO
4

+ 4H
+
+ 3e MnO
2
+ 2H
2
O (2) E
0
2
= 1,7 V
Ly (2) (1) ta c: MnO
2
4

+ 4H
+
+ 2e MnO
2
+ 2H
2
O
L na phn ng ca cp MnO
2
4

/MnO
2
cn xc nh E
0
.
Ta c:
0 0 0 0 0 0
3 2 1 3 2 1
G G G 2FE 3FE ( FE ) = =
Do :
0 0
0 2 1
3
3E E 3.1, 7 1.0, 56
E 2, 27(V)
2 2

= = =
* i vi cp MnO
2
/Mn
3+
ta c:
81
Mn
3+
+ 1e Mn
2+
(4) E
0
4
= 1,51 V
MnO
2
+ 4H
+

+ 2e Mn
2+
+ 2H
2
O (5) E
0
5
= 1,23 V
Ly (5) (4) ta c: MnO
2
+ 4H
+

+ e Mn
3+
+ 2H
2
O (6) Ta c:
0 0 0
6 5 4
G G G = -F. E
0
6
= - 2.F. E
0
5
- (-F. E
0
4
)
Do : E
0
6
=
0 0
5 4
2.E E 2.1, 23 1, 51 + = + = 0,95 V
Bi 9:
AgCl

Ag
+
+ Cl
-
T
AgCl
Ag Ag
+
+ 1e -
0
Ag / Ag
E
+
= -0,8V
AgCl + e Ag + Cl
-

0
AgCl / Ag
E 0, 22V =
T hp cc bn phn ng ta c: AgCl

Ag
+
+ Cl
-
E
0
= - 0,8 + 0,22 = -0,58 V.
Ta c:
0 0
pin
0
G nFE
G RTln K
=
=
RTlnK=nF.E
0
pin
lgK= nE
0
pin
/0,059= 1. (-0,58)/0,059
K =1,47.10
-10
.
Bi 10:
Khi trn ba dung dch trn vi nhau, nng ca cc ion ban u khi mi trn l:
2+ 2+
3+
0,3 0,06
[Cu ]= 0,1M; [Fe ]= 0, 02M;
3 3
0,03
[Fe ]= 0, 01M.
3
= =
=
2+ 2
o 2+
Cu / Cu Cu / Cu
0, 059 0,059
E E lg[Cu ]= 0,34+ lg0,1
2 2
+
= +
3+ 2 3 2
3+
o
2+ Fe / Fe Fe / Fe
0, 059 [Fe ] 0, 01
E E lg = 0,77+0,059.lg
1 [Fe ] 0, 02
+ + +
= +
Tnh
2+
Cu / Cu
E :

2+
Cu / Cu
E = 0,3105V
Tnh
3+ 2
Fe / Fe
E
+
:
82

3+ 2
Fe / Fe
E
+
= 0,75224V

2+
Cu / Cu
E <
3+ 2
Fe / Fe
E
+
Tnh oxi ha ca Fe
3+
mnh hn Cu
2+
Cn bng cho
phn ng theo chiu thun.
Sc in ng ca phn ng:
E
p
=
3+ 2
Fe / Fe
E
+
-
2+
Cu / Cu
E = 0,75224-0,3105 = 0,44174V.
Bi 11:
a. Cu + Cu
2+
+ 2Cl
-

2CuCl
0,1 0,2
* Xt cp : Cu
2+
+ 1e Cu
+
c [Cu
+
] =

Cl
K
s
=
2 , 0
10
7
= 5.10
-7

E (Cu
2+
/Cu
+
) = E
0
(Cu
2+
/Cu
+
) + 0,059.lg
] [
] [
2
+
+
Cu
Cu
= 0,15 + 0,059 lg
7
10 . 5
1 , 0

= 0,463 V
* Xt cp: Cu
+
+1e Cu
E(Cu
+
/Cu) = E
0
(Cu
+
/Cu) + 0,059 lg ] [
+
Cu = 0,52 + 0,059lg5.10
-7
= 0,148 V.
So snh thy: E(Cu
2+
/Cu
+
) > E (Cu
+
/Cu) phn ng xy ra theo chiu nghch.
b. Ta c cc cn bng:
Cu
2+
+ 1e Cu
+
K
1
= 10
0,15/0,059
= 10
2,54

Cu Cu
+
+ 1e K
2
= 10
-0,52/0,059
= 10
-8,81
2Cu
+
+ 2Cl
-

2CuCl (K
s
-1
)
2
= 10
14
T hp cc cn bng ta c:
Cu + Cu
2+
+ 2Cl
-

2CuCl K = 10
14
.10
2,54.
10
-8,81
= 10
7,73

Cu + Cu
2+
+ 2Cl
-

2CuCl
83
0,1 x 0,2 2x
Ta c:
3
) 1 , 0 ( 4
1
) 2 2 , 0 )( 1 , 0 (
1
x x x
=


[Cu
2+
] = 0,1 x = 1,67.10
-3
; [Cl
-
] = 2. (0,1 x) = 3,34.10
-3
(M)
Bi 12:
(a) Zn
2+
+ 2e Zn
E
1
=
2 2
0 2
Zn / Zn Zn / Zn
0, 059
E E lg Zn
2
+ +
+
( = +

= - 0,76 + (0,059/2).lg0,1 = - 0,7895 V
Ag
+
+ e Ag
E
2
=
0
Ag / Ag Ag / Ag
0, 059
E E lg Ag
1
+ +
+
( = +

= + 0,8 + 0,059.lg0,1 = 0,741 V
E
1
< E
2
nn in cc km l cc m v in cc bc l cc dng. S pin
in nh sau: (-) Zn , Zn(NO
3
)
2
0,1M ,, AgNO
3
0,1M , Ag (+)

b. Ti (-) c s oxi ha Zn 2e Zn
2+

Ti (+) c s kh Ag
+
: Ag
+
+ e Ag
Phn ng tng qut khi pin lm vic:
Zn + 2Ag
+
Zn
2+
+ 2Ag
c.
E
pin
= E
2
E
1
= 0,741 (- 0,7895) = 1,5305 V

d. Khi pin ngng hot ng th E
pin
= 0
Gi x l nng M ca ion Ag
+
gim i trong phn ng khi ht pin. Ta c:

2 2
0 2
Zn / Zn Zn / Zn
0, 059
E E lg Zn
2
+ +
+
( = +


84

0
Ag / Ag Ag / Ag
0, 059
E E lg Ag
1
+ +
+
( = +


E
pin
=
( ) 2 2
2
0 0
Ag / Ag Zn / Zn Ag / Ag Zn / Zn 2
Ag
0, 059
E E E E lg
2
Zn
+ + + +
+
+
(

= +
(


( )
2
pin
0,1 x
0, 059
E 0 lg 1, 53
x
2
0,1
2

= =
+

( )
2
51,86
0,1 x
10 0
x
0,1
2


+

x 0,1M

2
x
Zn 0,1 0,15M
2
+
( = +

;
51,86 27
x
Ag 0,1 .10 4, 55.10 M
2
+
| |
( = +
|

\


B. Bi tp t luyn

Bi 1: Nc oxy gi H
2
O
2
c th b kh thnh nc vi th chun l E
0
(H
2
O
2
/H
2
O
) =1,77V. Xt dung dch H
2
O
2
nng 1 mol/l.
1. Vit na phn ng oxy ha kh ng vi s kh ca nc oxy gi thnh nc.
2. Th oxy ha kh E ca cp H
2
O
2
/H
2
O ph thuc nh th no vo pH (trong
khong pH t 0 n 5)
3. V th ca E ph thuc vo pH.
4. Bit rng pH trong khong t 0 n 2, cc ion Fe
2+
v Fe
3+

tn ti trong dung
dch v E(Fe
3
/Fe
2+
) = E
0
(Fe
3+
/Fe
2+
) = 0,77V. Chng t rng ti pH = 1 th ion
Fe
2+
b oxi ha bi H
2
O
2
.
Bi 2:
1. Th chun ca cp Cu
2+
/Cu bng 0,34 V. Mt dy Cu nhng vo dung dch
CuSO
4
10
-2
mol/l. Tnh th in cc.
85
2. Ha tan 0,1 mol NH
3
vo 100 ml dung dch trn (b qua s thay i v th
tch) v chp nhn rng ch xy ra phn ng :
Cu
2+
+ 4NH
3
[Cu(NH
3
)
4
]
2+

Th in cc o c gim i 0,4V. Hy xc nh hng s bn ng (II)
tetramin.
Bi 3:
Dung dich A gm AgNO
3
0,050 M v Pb(NO
3
)
2
0,100 M.
1. Tnh pH ca dung dch A.
2. Thm 10 mL KI 0,250 M v HNO
3
0,200 M vo 10 mL dung dch A. Sau
phn ng ngi ta nhng mt in cc Ag vo dung dch B va thu c v
ghp thnh pin (c cu mui tip xc hai dung dch) vi mt in cc c Ag
nhng vo dung dch X gm AgNO
3
0,010 M v KSCN 0,040 M.
a) Vit s pin.
b) Tnh sc in ng E
pin
ti 25
o
C.
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng.
Cho bit: Ag
+
+ H
2
O

AgOH + H
+
(1) ; K
1
= 10
-11,70

Pb
2+
+

H
2
O PbOH
+
+ H
+
(2) ; K
2
= 10
-7,80

Ch s tch s tan pK
s
: AgI l 16,0; PbI
2
l 7,86; AgSCN l
12,0.
E
o
(Ag
+
/Ag) = 0,799 V; (RT/F) ln = 0,0592 lg
3. E
pin
s thay i ra sao nu:
a) Thm mt lng nh NaOH vo dung dch B.
b) Thm mt lng nh Fe(NO
3
)
3
vo dung dch X.

86
Bi 4: Cho cc in cc sau:
Cu , Cu
2+
(0,2 M); Cu , Cu
2+
(1 M); Pt , Fe
2+
(0,4M), Fe
3+
(0,6 M); Ag, AgCl ,
Cl
-
(0,1 M);
Pt, H
2
(p = 0,5 atm) , H
+
(0,1 M); Pt, Cl
2
(p = 2 atm) , Cl
-
(0,5 M).
1. Tnh th in cc ca cc in cc 25
o
C. Bit: E
o
(Cu
2+
/Cu) = + 0,34 V;
E
o
(Fe
3+
/Fe
2+
) = + 0,77 V, E
o
(AgCl/Ag+Cl
-
) = + 0,224 V, E
o
(Cl
2
/2Cl
-
) = + 1,36 V.
2. Vi cc in cc cho, c th lp c nhng pin no? (Vit s pin theo
qui c ca IUPAC). Tnh sc in ng ca pin. Vit cc phn ng in cc
v phn ng xy ra khi pin hot ng.
Bi 5: Cho cc phn ng sau din ra trong cc pin in:
1. Pb + 2 Ag
+
(aq)
Pb
2+
(aq)
+ 2 Ag
2. Cu
+
(aq)
+ Fe
3+
(aq)

Cu
2+
(aq)
+ Fe
2+
(aq)

3. Cu
2+
(aq)
+ H
2 (aq)
Cu + 2 H
+
(aq)

4. Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(r)

5. 2Ag + Cl
2 (k)
2AgCl
(r)

Hy vit s pin in v cho bit chiu ca dng in mch ngoi.
Bi 6: C 2 bnh: bnh 1 ng 0,5 lit dung dch hn hp Fe
2+
0,2 M v Fe
3+
0,1 M;
bnh 2 ng 1,0 lit dung dch hn hp Fe
2+
0,1 M v Fe
3+
0,2 M. Nhng 2 thanh Pt
vo 2 bnh v cho cu mui tip xc vi 2 dung dch (ngi ta thit lp mt pin
nng ).
1. Ch r cc tnh ca 2 in cc.
2. Vit s pin in v tnh sc in ng ca pin .
Ni 2 in cc bng dy dn
3. Vit cc phn ng in cc v phn ng xy ra khi pin hot ng.
4. Tnh nng ion Fe
2+
v Fe
3+
trong cc bnh khi pin ngng hot ng v
in lng i qua dy dn.
Bi 7: Cho E
o
(Ag
+
/Ag) = + 0,799 V, K
s
(AgCl) = 1,8.10
-10
, E
o
(Cu
2+
/Cu) = + 0,34
V.
1. Tnh th ca in cc Ag, AgCl / KCl (1,0 M)
2. Xc nh chiu ca dng in trong pin to thnh bi in bc clorua trn
v in cc ng tiu chun. Vit phng trnh ca phn ng xy ra trong
pin v tnh hng s cn bng ca phn ng .
87
Bi 8: Xc nh tch s tan ca AgBr bit rng pin c to thnh bi in cc
hiro tiu chun v in cc Ag,AgBr/Br
-
(0,1 M) c sc in ng bng 0,14 V.
Cho E
o
(Ag
+
/Ag) = 0,8 V.
Bi 9: xc nh hng s in ly ca CH
3
COOH, ngi ta thit lp mt pin:
(-) Pt, H
2
(p = 1 atm), CH
3
COOH (0,01 M),, H
+
(1,0 M) , H
2
(p = 1 atm), Pt (+)
Sc in ng ca pin bng 0,1998 V ( 25
o
C).
Tnh hng s in ly ca CH
3
COOH.
Bi 10: Ngi ta dng dng in 15 A kt ta Ni trong b m cha NiSO
4
. Ni
v H
2
cng c to thnh cc m. Bit rng 60% in lng c dng gii
phng Ni.
1. C bao nhiu gam Ni s kt ta trn in cc trong mt gi?
2. dy ca lp m l bao nhiu cm nu cc m l mt l kim loi hnh
vung cnh 4 cm v s kt ta xy ra trn hai mt ca l kim loi. Bit khi
lng ring ca Ni l 8,9 g/cm
3
.
Bi 11: Cho cc in cc sau:
Cu , Cu
2+
(0,2 M); Cu , Cu
2+
(1 M); Pt , Fe
2+
(0,4M), Fe
3+
(0,6 M); Ag, AgCl , Cl
-

(0,1 M); Pt, H
2
(p = 0,5 atm) , H
+
(0,1 M); Pt, Cl
2
(p = 2 atm) , Cl
-
(0,5 M).
3. Tnh th in cc ca cc in cc 25
o
C.
Bit E
o
(Cu
2+
/Cu) = + 0,34 V E
o
(AgCl/Ag, Cl
-
) = + 0,224 V, cc gi tr E
o

khc tra trong bng).
4. Vi cc in cc cho, c th lp c nhng pin no? (Vit s pin
theo qui c ca IUPAC). Tnh sc in ng ca pin. Vit cc phn ng
in cc v phn ng xy ra khi pin hot ng.
Bi 12: C 2 bnh: bnh 1 ng 0,5 lit dung dch hn hp Fe
2+
0,2 M v Fe
3+
0,1
M; bnh 2 ng 1,0 lit dung dch hn hp Fe
2+
0,1 M v Fe
3+
0,2 M. Nhng 2 thanh
Pt vo 2 bnh v cho cu mui tip xc vi 2 dung dch (ngi ta thit lp mt
pin nng ).
5. Ch r cc tnh ca 2 in cc.
6. Vit s pin in v tnh sc in ng ca pin .
Ni 2 in cc bng dy dn
88
7. Vit cc phn ng in cc v phn ng xy ra khi pin hot ng.
8. Tnh nng ion Fe
2+
v Fe
3+
trong cc bnh khi pin ngng hot ng v
in lng i qua dy dn.
Bi 13: Cho cc phn ng sau din ra trong cc pin in:
6. Zn + Br
2 (aq)
Zn
2+
(aq)
+ 2 Br
-
(aq)

7. Pb + 2 Ag
+
(aq)
Pb
2+
(aq)
+ 2 Ag
8. Cu
+
(aq)
+ Fe
3+
(aq)

Cu
2+
(aq)
+ Fe
2+
(aq)

9. Cu
2+
(aq)
+ H
2 (aq)
Cu + 2 H
+
(aq)

10. Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(r)

11. Ag + Cl
2 (k)
AgCl
(r)

Hy vit s pin in v cho bit chiu ca dng in mch ngoi.
Bi 14:
1. Zn v Cu c phn ng vi dung dch HCl 1,0 M 25
o
C hay khng?
2. Tai sao Fe phn ng vi dung dch HCl ch cho ra sn phm l FeCl
2
m
khng phi l FeCl
3
.
Bi 15: D on chiu ca cc phn ng oxi ho - kh sau:
1. Fe + Cu
2+
Fe
2+
+ Cu
2. 2Fe
2+
+ Cu
2+
2Fe
3+
+ Cu
3. Fe
2+
+ Ag
+
Fe
3+
+ Ag
4. 2 MnO
4
-
+ 10 Cl
-
+ 16 H
+
2Mn
2+
+ 5Cl
2
+ 8H
2
O
5. 2 Fe
3+
+ 2 Cl
-
2 Fe
2+
+ Cl
2

6. 2 Fe
3+
+ 2 I
-
2 Fe
2+
+ I
2

Bi 16:
1. Xc nh chiu ca phn ng:
2 Hg + 2 Ag
+
2 Ag + Hg
2
2+
cc iu kin sau:
a) [Ag
+
] = 10
-4
M; [Hg
2
2+
] = 0,1 M
b) [Ag
+
] = 0,1 M; [Hg
2
2+
] = 10
-4
M
2. iu ch Cl
2
trong phng th nghim, ngi ta cho dung dch HCl c
tc dng vi K
2
Cr
2
O
7
m khng dng dung dch HCl long. Gii thch ti
sao?
Bit: E
o
(Cl
2
/2Cl
-
) = E
o
(Cr
2
O
7
2-
/Cr
3+
) = 1,36 V
Bi 17: nh gi kh nng phn ng gia Fe
3+
v I
-
d trong:
89
1. Dung dch c pH = 0
2. Dung dch c NaF d.
Bit: E
o
(Fe
3+
/Fe
2+
) = 0,77 V; E
o
(I
3
-
/3I
-
) = 0,55 V; p(FeF
3
) = -12.
Bi 18: nh gi kh nng ho tan ca Ag trong KCN d khi c O
2
khng kh.
Bit:
E
o
(Ag
+
/Ag) = 0,80 V; E
o
(O
2
/H
2
O) = 1,23 V
Ag
+
+ 2 CN
-
Ag(CN)
2
-
= 10
21
.
Bi 19: Sc H
2
S vo dung dch FeCl
3
0,10 M n bo ho, c hin tng g xy
ra? Bit:
pK
s
(FeS) = 17; E
o
(Fe
3+
/Fe
2+
) = 0,77 V; E
o
(S/H
2
S) = 0,14 V; nng H
2
S
bo ho l 0,1 M v H
2
S c pK
1
= 7,0; pK
2
= 12,9.
Bi 16: Kh nng kh ca Fe
2+
trong mi trng axit hay trong mi trng kim
mnh hn, v sao? Bit:
E
o
(Fe
2+
/Fe) = - 0,44 V; E
o
(Fe
3+
/Fe) = - 0,04 V;
K
s
(Fe(OH)
2
) = 1,65.10
-15
; K
s
(Fe(OH)
3
) = 3,8.10
-38

Bi 20:
1. Ion Cu
2+
c oxi ho c ion I
-
?
2. Bng thc nghim, ngi ta quan st c phn ng:
Cu
2+
+ 2 I
-
CuI

+ I
2

Tnh hng s cn bng ca phn ng trn
Bit: E
o
(Cu
2+
/Cu
+
) = + 0,16 V; E
o
(I
2
/2I
-
)

= +0,54 V v pK
s
(CuI) = 12.
Bi 21: Mt dung dch ban u cha [Fe
2+
] = [Fe
3+
] = 0,10 M. pH ca dung dch
c iu chnh bng 10 (dung dch A).
1. Tnh nng cc ion Fe
2+
v Fe
3+
trong dung dch A, t suy ra th kh
ca cp Fe
3+
/Fe
2+
trong dung dch .
2. Ngi ta a mt lng d mt st vo dung dch A (pH vn c gi bng
10). Hin tng g xy ra. trng thi cn bng, nng cc ion Fe
2+
v
Fe
3+
l bao nhiu v thnh phn ca kt ta?
90

Cu hi m rng v ng dng: Hy tho lun v cu to ca cc loi pin v
acquy c trn th trng:
1) pin kh Le Clanch: Con Th, Con , ...
2) pin kh AA, AAA, ....
3) cc loi in kh 12 V (loi dng cho micro khng dy, chung ca, ...)
4) cc loi pin sc li c nh pin cho my tnh, in thoi, ...

















91
Chuyn 4
CU TO NGUYN T V BNG TUN HON
T Ha hc, trng THPT chuyn Hong Vn Th, Ha Bnh

PHN I: l thuyt
A. Bng h thng tun hon cc nguyn t ho hc
I. Nguyn tc sp xp cc nguyn t ho hc
Theo chiu in tch ht nhn (Z) tng dn
II. Cu trc bng HTTH
1. vung: Cha d liu v 1 nguyn t ho hc
- K hiu ho hc
- Tn nguyn t
- Khi lng nguyn t trung bnh hay nguyn t khi
M A =p + n = Z + N
- S th t = Z = e = p
- Cu hnh

- m in
VD:
11
Na : |Ne|3s
1

19
K : |Ar|4s
2

92
2. Chu k: L dy cc s nguyn t c xp theo hng ngang v c s lp bng
nhau.
*S th t ca chu k = s lp
VD:
Chu k 1:
1
H
2
He 2 ng. t
Chu k 2:
3
Li
4
Be
5
B
6
C
7
N
8
O
9
F
10
Ne 8 ng. t
Chu k 3:
11
Na
12
Mg
13
Al
14
Si
15
P
16
S
17
Cl
18
Ar 8 ng. t
Chu k 4:
19
K
20
Ca
35
Br
36
Kr 18 ng. t
Chu k 5:
53
I
54
Xe 18 ng. t
Chu k 6: 32 ng. t
Chu k 7: ang x/

Chu k 1, 2, 3: cc nguyn t xp vo 1 hng gi l chu k nh
Chu k 47: c nhiu nguyn t xp vo 2 hng gi l chu k ln
Ring chu k 6: C 14 nguyn t ging Lantan c tch ring xung pha di
bng h La.
Tng t chu k 7 h Actini c xp ra gi l phn ngoi bng.
3. Nhm: L dy cc nguyn t c xp theo ct dc v c s electron lp ngoi
cng bng nhau
a. Nhm A: Gm cc nguyn t m electron cui cng (theo mc nng lng) c
xp vo phn lp s hoc p (gi l nguyn t h s, h p)
*S th t nhm A bng s electron lp ngoi
VD:
93
b. Nhm B: Gm cc nguyn t m electron cui cng (theo mc nng lng) c
xp vo phn lp d hoc f (gi l nguyn t h d, h f)
*S th t nhm B bng tng s electron lp ngoi v s electron phn lp st
ngoi cng nhng cha bo ho.
- Nu bo ho th s electron phn lp st ngoi tnh bng 0
- Nu tng s electron st ngoi + phn lp st ngoi = 9 hoc 10 th nguyn t s
thuc nhm 8
*Lu :
1. Trong bng HTTH c:
- Cc vung
- 7 chu k
- 16 nhm (8 nhm A, 8 nhm B)
- Phn ngoi bng (h La, h Ac)
2. Cc nguyn t thuc chu k 1, 2, 3 chc chn thuc phn nhm chnh.
Cc nguyn t c Z > 21 th c th thuc phn nhm chnh hoc phn nhm ph.
3. Nu 2 nguyn t cng 1 phn nhm chnh v chu k k tip nhau th Z chnh
lch 8 hoc 18 hoc 32.

B. S bin thin v tnh cht n cht - Thnh phn v tnh cht cc hp cht
I. S bin thin cc i lng
1. Nng lng ion ho
a. nh ngha: Nng lng cn thit tch 1electron ngoi cng ra khi nguyn
t ca n trng thi kh(hi) c gi l nng lng ion ha ca nguyn t.
94
b. Bin thin nng lng ion ho
b
1
. Trong mt chu k i t tri sang phi: nng lng ion ho tng dn
*Gii thch: Trong 1 chu k khi i t tri sang phi th cc nguyn t c cng s
lp electron nhng Z tng ln lc ht gia ht nhn vi electron ngoi cng tng
ln.
Kh nng tch ra electron khi nguyn t cng kh nng lng ion ho tng
*Lu : 1 s chu k (nh chu k 2 ) c trng hp bt thng?
b
2
. Trong 1 phn nhm chnh: i t trn xung di nng lng ion ho gim dn
Trong 1 phn nhm chnh: i t trn xung di s lp tng dnkhong cch t
ht nhn n electron lp ngoi cng tng dn lc ht gia ht nhn v electron
lp ngoi gimnng lng ion ho gim
2. Bn knh nguyn t (r)
a. nh ngha: tu tng loi hp cht.
Hiu mt cch n gin: r
nt
khong cch t ht nhn n ngoi cng
b. Bin thin
b
1
. Trong 1 chu k i t phi sang tri th r gim
*Gii thch: Trong 1 chu k i t tri qua phi cc nguyn t c cng s lp e
nhng Z tng lc ht gia ht nhn v e ngoi cng tngkhong cch nhn v
lp ngoi cng gimr gim
b
2
. Trong phn nhm chnh: i t trn xung di th r tng
*Gii thch: v s lp tng dn.
3. m in: ( ) - Capa
95
a. nh ngha: m in l i lng c trng cho kh nng ht v pha
nguyn t ca 1 nguyn t ( tng th kh nng ht tng)
b. Bin thin
b
1
. Trong 1 chu k t tri qua phi: tng
b
2
. Trong phn nhm chnh: t trn xung di: gim
4. i lc electron: i lc e ca mt nguyn t l nng lng qu trnh nguyn t
ca nguyn t ( trng thi kh)kt hp thm 1e to thnh ion m.
II. S bin thin tnh cht n cht
a. Tnh kim loi: c trng l kh nng nhng (tnh kh)
Tnh phi kim: c trng l kh nng nhn (tnh oxi ho)
Kh cho O nhn
b. S bin thin
a. Trong 1 chu k: i t tri sang phi: tnh kim loi gim, tnh phi kim tng
*Gii thch:
- I kh nhng, d nhn tnh kim loi , tnh phi kim
- kh nng ht Tnh phi kim kim loi
- r lc ht gia ht nhn v ngoi cng kh nng tch tnh phi
kim
+) Trong 1 chu k i t tri sang phi th cc nguyn t c cng s lp nhng
Z lc ht gia ht nhn v ngoi cng kh nng tch tnh kim
loi phi kim .

VD: Chu k 3
96

11
Na
12
Mg
13
Al
14
Si
15
P
16
S
17
Cl
KL
kim
Kim
th
Lng
tnh
Phi
kim
yu
Phi
kim
Phi
kim
Phi
kim
Rt
mnh
Mnh Yu
Trung
bnh
Mnh
Rt
mnh
+ H
2
O
kh t/d
H
2
O

T n h k i m l o i g i m
T n h p h i k i m t n g

*Lu : Trong 1 chu k (tr chu k 1) u bt u l 1 kim loi mnh (kim loi
in hnh kim) kt thc l 1 phi kim mnh (phi kim in hnh- Halgen)
b. Trong 1 phn nhm chnh: T trn xung di tnh kim loi , phi kim
Gii thch: Theo 4 cch nh trn: theo I ; Theo ; Theo r
+) S lp phi kim
VD: Phn nhm chnh II (kim loi kim th)
Be kim loi lng tnh
Mg kim loi trung bnh (khng tc dng H
2
O)
Ca kim loi mnh (tc dng
2
H O)
Ca+2H
2
O=Ca(OH)
2
+ H
2
T

n
h

k
i
m

l
o

n
h

p
h
i

k
i
m


Sr kim loi rt mnh
97
Ba
Ra
*


VD: Phn nhm chnh IV
C phi kim trung bnh
Sr phi kim yu
Ge kim loi yu
Sn kim loi trung bnh
T

n
h

k
i
m

l
o

n
h

p
h
i

k
i
m


Pb kim loi mnh
III. Xt v cc hp cht
1. Oxit : X
2
O
n

- X nguyn t ho hc
- n s th t ca phn nhm chnh
- X
2
O
n
l cng thc cao nht
VD:
11
Na Na
2
O
12
Mg MgO
16
S 1s2
2
s2
2
p
6
3s
2
3p
4
SO
3

11
Cl 1s2
2
s2
2
p
6
3s
2
3p
5
Cl
2
O
7
2. Hiroxit
98
X: nguyn t ho hc
n: s th t ca phn nhm chnh
Baz: Xkim loi
X(OH)
n

X(OH)
n

Hyroxit
Axit c oxi: Xphi
kim
VD:
11
Na: [Ne]3s
1
NaOH
13
Al: [Ne]3s
2
3p
1
Al(OH)
3
16
S: [Ne]3s
2
3p
4
S(OH)
6
2
-2H O
2 4
H SO
S O H
O H
OH
OH
OH
OH
S
OH
OH
O
O
H
2
SO
4
-2 H
2
O.

7
N: [Ne]2s
2
2p
3
N(OH)
5
2
-2H O
3
HNO
15
P: [Ne]3s
2
3p
3
P(OH)
5
2
2
-H O
3 4
-2H O
3
H PO
HPO


3. Hirua: L hp cht nh nguyn t (gm H v 1 nguyn t ho hc khc)
a. Nu nguyn t l kim loi th cng thc l: MH
n

M: k hiu nguyn t
H: hyr
n: s th t
Vi MH
n
:
- Tn: M + hyrua
99
- Cht rn
- D tan vo H
2
OBaz + H
2

* Vi nguyn t kim loi th ho tr trong oxit cao nht bng ho tr ca hp cht
Hidrua bng s th t phn nhm chnh.
VD:
11
Na: [Ne]3s
1
NaH
rn
(Natri Hirua)
b. Nu l phi kim th cng thc l XH
8-n
(n=s th t phn nhm chnh)
Vi XH
8-n

- Tn: Hiro + tn X+ ua
- Kh
- D tan vo H
2
O dung dch axit hoc dung dch baz
* Vi nguyn t phi kim: Ho tr trong oxit cao nht + ho tr trong hp cht vi
Hydrua = 8
VD:
17
Cl: [Ne]3s
2
3p
3
oxit cao nht Cl
2
O
7

Hp cht vi H: H
2
+ Cl
2
HCl

4. S bin thin tnh cht cc hp cht trong chu k v phn nhm chnh
*Tnh cht ca cc hp cht bin thin theo tnh cht ca cc nguyn t trong
hp cht
Nu nguyn t l kim loi hp cht c tnh cht Baz: Oxit Baz; Hiroxit Baz;
Hirua Baz (rn)
Nguyn t l phi kim hp cht c tnh Axit: Oxit Axit; Hiroxit l axit; Hirua
(kh)
100
*Nu tnh kim loi gim, tnh phi kim tng th hp cht c tnh Baz gim,
axit tng.
VD: Chu k 3
Tnh kim loi , tnh phi kim
11
Na
12
Mg
13
Al
14
Si
15
P
16
S
17
Cl
Hiroxit: Tnh baz gim, tnh axit tng.
NaOH Mg(OH)
2
Al(OH)
3
Si(OH)
4
P(OH)
5
S(OH)
6
Cl(OH)
7
-H
2
O -H
2
O -2H
2
O -3H
2
O
HAlO
2
.H
2
O H
2
SiO
3
H
3
PO
4
H
2
SO
4
HClO
4
Baz rt
mnh
Baz yu Lng tnh Axit yu Axit
trung
bnh
Axit
mnh
Axit rt
mnh

C. Tng kt s bin thin trong HTTH
* Trong bng HTTH: theo chiu Z th lun c s lp i lp li (tun hon) v cu
hnh electron, tnh cht n cht, v cng thc, tnh cht ca cc hp cht.
* S bin thin ca chu k 2 th no th cc chu k khc cng tng t
(Tuy nhin s bin thin ca cc i lng v cc tnh cht trong chu k ln thng
chm hn cc chu k nh)
S bin thin ca nhm IA th no th cc nhm A khc cng tng t.
D. nh lut tun hon cc nguyn t ho hc
Theo chiu in tch ht nhn tng dn: Tnh cht n cht, thnh phn v tnh cht
cc hp cht bin thin tun hon.
101
* Nguyn nhn ca s bin thin tun hon l do s bin thin tun hon v cu
hnh electron.
E. ngha ca cu hnh electron
1. T cu hnh electronsuy ra v tr ca cc nguyn t
2. T cu hnh electron suy ra Tnh cht n cht, thnh phn v tnh cht cc
hp cht.
3. T cu hnh electron s so snh c tnh cht ca cc nguyn t.

Phn II: bi tp vn dng
Bi 1
Cho cc nguyn t sau y: Cl; Al; Na; P , cn c vo s bin thin tnh cht
ca cc nguyn t trong mt chu k v trong 1 nhm ca bng tun hon.
a) Hy sp xp theo th t tng dn ca bn knh nguyn t i vi cc
nguyn t trn.
b) Cho bit th t tng dn v m in ca cc nguyn t kho st ni trn.
*HD:
Trong 1 chu k , khi i t tri qua phi:
a) bn knh nguyn t gim dn:
r: Na > Al > P > Cl
b) m in tng dn:
: Na < Al < P < Cl
Bi 2
Cn c vo cu hnh electron ca Na
+
(Z = 11) v Ne (Z= 10), hy so snh
bn knh ca chng.
*HD:
102
Vit cu hnh e ca cc ht ri so snh:
- s lp electron.
- Nu cng s lp electron s so snh in tch ht nhn Z.
Na: 1s
2
2s
2
2p
6
3s
1
Na
+
: 1s
2
2s
2
2p
6

Ne: 1s
2
2s
2
2p
6

Na
+
v Ne c cng cu hnh e , nhng Z ca Na > Ne; r: Na
+
< Ne.
Bi 3
Ba nguyn t X, Y, Z trong cng mt chu k c tng s hiu nguyn t l 39.
S hiu ca nguyn t Y bng trung bnh cng s hiu ca nguyn t X v Z.
Nguyn t ca 3 nguyn t ny hu nh khng phn ng vi H
2
O iu kin
thng.
a) Hy xc nh v tr cc nguyn t trong bng tun hon cc nguyn t ho
hc. Vit cu hnh e ca nguyn t v gi tn tng nguyn t.
b) So snh m in, bn knh nguyn t ca cc nguyn t .
c) So snh tnh baz ca cc hiroxit.
*HD:
a) S hiu nguyn t: Z
X
, Z
Y
, Z
Z

Gii h phng trnh Z
y
= 13 Y: Al (nhm)
Z
X,
, Z
Y
cng chu k nn Z
x
= 11 hoc 12.
Z
X
= 11 X: Na (tc dung vi H
2
O) loi
Z
X
= 12 X: Mg( magi)
Z
z
= 14 Z: Si (silic)
b) : Mg < Al < Si
r: Mg > Al > Si
103
c) Tnh baz: Mg(OH)
2
> Al(OH)
3
> Si(OH)
4

Bi 4
Ngi ta bit rng Sr (Z = 38) khi mt 2e s c cu hnh electron bn vng;
trong khi nguyn t Fe(Z = 26) li cho 2 dng cu hnh electron bn vng khi
mt electron. Hy vit cu hnh electron cho 3 trng hp trn v ch r s electron
c thn cho tng trng hp.
*HD:
S e c thn
38
Sr: [Kr]5s
2
Sr
2+
: [Kr] 0
26
Fe: [Ar]3d
6
4s
2
Fe
2+
: [Ar]3d
6
4
Fe
3+
: [Ar]3d
5
5
Bi 5
Ion X
3+
c phn lp electron ngoi cng l 3 d
2
: .
- Vit eu hnh electron ca nguyn t X v ion X
3+
:
- Xc nh in tch ht nhn ca X
3+
;
- Xc nh chu k, phn nhm ca X .
- Hai electron 3d
2
ng vi nhng gi tr no ca 4 s lng t ?
*HD:
Cu hnh e: X
3+
: 1s
2
2s
2
2p
6
3s
2
3d
2

X: 1s
2
2s
2
2p
6
3s
2
3d
3
4s
2

X: Z = 23, chu k 4, nhm VB
Cc e c thn: + n = 3, l = 2, m
l
= -2, m
s
= +1/2
104
+ n = 3, l = 2, m
l
= -1, m
s
= +1/2
Bi 6
a) Vit cu hnh electron trng thi c bn cho cc nguyn t sau:
Mg(Z = 12); Ca(Z = 20); Sr(Z = 38); Zn(Z = 30); Cd(Z = 48).
b) Cho cc gi tr th ion ha th nht (n v kJ/mol) : 548; 585; 736; 903.
Hy gn cc gi tr ni trn cho cc nguyn t cu hi (a)
*p s:
b) I
1
(KJ/mol) Nguyn t
548 Sr
585 Ca
736 Mg
903 Zn
864 Cd
Bi 7
Trong mt chu k v trong mt nhm A, nng lng ion ha th nht (I
1
,
kJ/mol) bin i nh th no?
Hy gii thch: - I
1
(B) < I
1
(Be)
- I
1
(O) < I
1
(N)
- I
1
(Si) = 786 ; I
1
(P) = 1012 ; I
1
(S) = 1000 v I
1
(Cl) = 1251
*HD:
Gii thch cc bt thng do: Be c cu hnh electron bo ha phn lp, cn N
v P c cu hnh electron na bo ha.
105
Bi 8
a) Rai l nguyn t th kim c Z = 88. Hy cho bit nguyn t th kim tip
theo s c s th t Z l bao nhiu ?
b) S nghin cu hin nay hng v s iu ch nhn to cc nguyn t c s
th t l 112, 118 v theo d kin cc nguyn t ny c mt bn tng i.
Hy gii thch iu da trn cu hnh in t ca chng.
*HD:
a) Nguyn t th kim tip theo nguyn t. Ra s c s th t :
Z = 88 + 14 + 10 + 2 + 6 = 120
(5f) (6d) (8s) (7p)
b)
112
Y c cu hnh : [Rn] 5f
l4
6d
10
7s
2
. phn lp 6d bo ho .

118
Z c cu hnh: [Rn] 5f
l4
6d
10
7s
2
7p
6
lp v c cu trc ca mt kh:tr.
Bi 9
Cho bit mt s gi tr nng lng ion ho th nht (I
1
, eV) : 5,14 ; 7,64 ;
21,58 ca Ne, Na, Mg v mt s gi tr nng lng ion ho th hai (I
2
, eV) : 41,07 ;
47,29 ca Na v Ne.
Hy gn mi gi tr I
1
, I
2
cho mi nguyn t v gii thch. Hi I
2
ca Mg nh
th no so vi cc gi tr trn? V sao?
*HD:
Ne (2s
2
, 2p
6
) cu hnh bn vng.
Na (2s
2
, 2p
6
, 3s
1
) c e 3s d tch ra khi nguyn t c cu hnh bn vng
I
1
ca Na nh hn I
1
ca Ne.
Mg (2s
2
, 2p
6
, 3s
2
) c in tch ht nhn ln hn so vi Na
nng lng I
1
ln hn I
1
ca Na.
106
Vy: I
1
(Na) = 5,14 ; I
1
(Mg) = 7,64 ; I
1
(Ne) = 21,58 .
Bi 10
Hp cht M to bi 2 nguyn t X v Y, cho bit:
- Tng s 3 loi ht trong nguyn t X l 52, ho tr cao nht ca X vi oxi
gp 7 ln ho tr ca X vi hir.
- Y thuc cng chu k vi X, c cu hnh electron: ...np
1
.
a) Xc nh s th t X, Y trong bng h thng tun hon v gi tn 2 nguyn
t.
b) Xc nh cng thc phn t, vit cng thc cu to ca M bit hiu m
in gia X v Y c gi tr tuyt i nh hn 1,77. Khi lng phn t ca M l
267.
*HD:
a) - Xc nh c Z = 17 X l Cl (clo).
- T d liu u bi xc nh c Y l Al.
b) T d liu u bi vi KLPT ca M l 264.
cng thc phn t M l:

Al
Cl
Cl
Cl
Cl
Al
Cl
Cl

Bi 11
Hp cht A c tng s electron trong phn t l 100. A c to thnh t
2 phi kim thuc cc chu k nh v thuc 2 nhm khc nhau. Xc nh cng thc
phn t ca A, bit rng tng s nguyn t cc nguyn t trong A l 6. M t cu
to phn t A (hnh dng, kiu lin kt).
*HD:
Gi 2 phi kim trong A l X v Y.
107
A ch c th l XY
5
hoc X
2
Y
4
(khng th l X
3
Y
3
v s thuc cng nhm).
Nu A l XY
5

X thuc nhm VA ; Y thuc nhm VIIA.
S n v in tch ht nhn trung bnh ca X, Y :
100
16, 7.
6
=
nu
X
Z < 16,7 X l photpho (N khng th to 5 lin kt)
Y
100 15
Z 17,
5

= = vy Y l clo.
Cng thc ca A l PCl
5
.
Nu Z
X
> 16,7 Z
Y
< 16,7 Y ch c th l F (Z
F
= 9) Z
X
+ 5.9 = 100
Z
X
= 55, loi v X thuc chu k ln.
Nu A l X
2
Y
4

X thuc nhm VA (ho tr 3).
Y thuc nhm VIA (ho tr 2).
Nu Z
X
< 16,7 X c th l N hoc P.
Nu X l N : 2.7 + 4Z
Y
= 100 Z
Y
=
100 14
4

loi.
Nu X l P : 2.15 + 4Z
Y
= 100 Z
Y
=
70
4
loi.
Nu Z
X
> 16,7 Z
Y
< 16,7 Y l oxi hoc lu hunh.
Nu Y l O : 2Z
X
+ 4.8 = 100 Z
X
= 34 (loi).
Nu Y l S : 2Z
X
+ 4.16 = 100 Z
X
= 18 (loi).
Vy cng thc ca A ch c th l PCl
5
.
PCl
5
c cu trc lng chp tam gic.
Nguyn t P tm tam gic u y lng thp.
108

Nguyn t P c lai ho sp
3
d.
Lin kt gia P v Cl l lin kt cng ho tr gia cc AO lai ho sp
3
d ca P vi
AO p ca nguyn t Cl (lin kt ).
Bi 12
Bit E
n
= -13,6.
2
2
n
Z
(n: s lng t chnh, Z: s n v in tch ht nhn).
1. Tnh nng lng 1e trong trng lc mt ht nhn ca mi h N
6+
, C
5+
,
O
7+
.
2. Qui lut lin h gia E
n
vi Z tnh c trn phn nh mi lin h no
gia ht nhn vi electron trong cc h ?
3. Tr s nng lng tnh c c quan h vi nng lng ion ho ca mi h
trn hay khng ? Tnh nng lng ion ho ca mi h.
*HD:
1. Theo u bi, n phi bng 1 nn ta tnh E
1
. Do cng thc l E
1
= 13,6 Z
2

(ev) (2)
Th t theo tr s Z: Z = 6 C
5+
: (E
1
) C
5+
= 13,6 x 6
2
= 489,6 eV
Z = 7 N
6+
: (E
1
) N
6+
= 13,6 x 7
2
= 666,4 eV
Z = 8 O
7+
: (E
1
) O
7+
= 13,6 x 8
2
= 870,4 eV
2. Quy lut lin h E
1
vi Z : Z cng tng E
1
cng m (cng thp). Qui lut ny
phn nh tc dng lc ht ht nhn ti e c xt: Z cng ln lc ht cng mnh
nng lng cng thp h cng bn, bn nht l O
7+
.
3. Tr nng lng c lin h vi nng lng ion ho, c th:
109
C
5+
: I
6
= (E
1
, C
5+
) = + 489, 6 eV.
N
6+
: I
7
= (E
1
, N
6+
) = + 666, 4 eV.
O
7+
: I
8
= (E
1
, O
7+
) = + 870,4 eV.
Bi 13
Trong nguyn t hoc ion dng tng ng c t 2 electron tr ln, electron
chuyn ng trong trng lc c to ra t ht nhn nguyn t v cc electron
khc. Do mi trng thi ca mt cu hnh electron c mt tr s nng lng. Vi
nguyn t Bo (s n v in tch ht nhn Z = 5) trng thi c bn c s liu nh
sau:
Cu hnh
electron
Nng lng (theo
eV)
Cu hnh
electron
Nng lng (theo eV)
1s
1
1s
2

1s
2
2s
1

-340,000
- 600,848
- 637,874
1s
2
2s
2

1s
2
2s
2
2p
1

- 660,025
- 669,800
Trong : eV l n v nng lng; du - biu th nng lng tnh c khi
electron cn chu lc ht ht nhn.
a) Hy trnh by chi tit v kt qa tnh cc tr s nng lng ion ho c th c
ca nguyn t Bo theo eV khi dng d kin cho trong bng trn.
c) Hy nu ni dung v gii thch qui lut lin h gia cc nng lng ion ho
.
*HD:
a) Tnh cc tr nng lng ion ho c th c ca Bo:
T cu hnh electron cho , ta xc nh c cc vi ht tng ng cng vi
tr nng lng nh sau:
Cu hnh
electron
Vi ht Nng lng
(theo eV)
Cu hnh
electron
Vi ht


Nng lng
(theo eV)
1s
1
B
4+
- 340,000 1s
2
2s
2
B
+
- 660,025
110
1s
2

1s
2
2s
1

B
3+
B
2+

- 600,848
- 637,874
1s
2
2s
2
2p
1
B - 669,800
C nh ngha: Nng lng ion ho (ca mt nguyn t) l nng lng t nht cn
tch 1 e khi nguyn t trng thi c bn m khng truyn thm ng nng
cho e .
Vy gia nng lng ca1 e trng thi c bn v nng lng ion ho I
tng
ng c lin h: I = - (1).
Vy vi s ion ho M
(k 1)+
- e

M
k+
; I
k
(2),
Ta c lin h: I
k
= - = - |E
M
(k -1)+ - E
M
k+ | (3)
Trong : k ch s e b mt (do s ion ho) ca vi ht c xt, c tr s t 1 n
n; do k+ ch s n v in tch dng ca ion M
k+
;
I
k
l nng lng ion ho th k ca nguyn t M c biu th theo (2).
Xt c th vi nguyn t Bo: v Z = 5 nn nguyn t c 5 e; vy k = 1 n 5.
p dng phng trnh (2) v (3), dng s d kin bng trn cho Bo, ta c:
* B
o
e

B
+
; I
1
( vy k = 1);
I
1
= - [ E
B
E
B
+] = ( 669,800 + 660,025 ). Vy I
1
= 9,775 eV .
* B
+
e

B
2+
; I
2
( vy k = 2);
I
2
= - [ E
B+
E
B
2+] = ( 660,025 + 637,874). Vy I
2
= 22,151 eV .
* B
2+
e

B
3+
; I
3
( vy k = 3);
I
3
= - [E
B
2+ E
B
3+] = ( 637,874 + 600,848). Vy I
3
= 37,026 eV .
* B
3+
e

B
4+
; I
4
( vy k = 4);
I
4
= - [E
B
3+ E
B
4+] = ( 600,848 + 340,000). Vy I
4
= 260,848 eV .
111
* B
4+
e

B
5+
; I
4
( vy k = 5);
I
5
= - [E
B
4+ E
B
5+] = ( 340,000 + 0,000). Vy I
5
= 340,000 eV .
b) T kt qu trn, ta thy c qui lut lin h cc tr nng lng ion ho ca
Bo nh sau I
1
< I
2
< I
3
< I
4
< I
5
(4).
Gii thch: Khi vi ht M
(k 1)+
mt thm 1 e to thnh M
k+
c s n v in tch
k+ ln hn (k 1) nn lc ht tc dng ln e tip theo trong vi ht M
k+
mnh hn
so vi trong M
(k 1)+
. Do phi tn nng lng ln hn tch 1 e tip theo khi
M
k+
; ngha l I
( k 1)
< I
k
nh c ch ra trong (4) trn y.
Bi 14
Trong bng di y c ghi cc nng lng ion ho lin tip I
n
(n = 1, ..., 6)
theo kJ.mol
1
ca 2 nguyn t X v Y
I
1
I
2
I
3
I
4
I
5
I
6

X 590 1146 4941 6485 8142 10519
Y 1086 2352 4619 6221 37820 47260
A v B l nhng oxit tng ng ca X v Y khi X, Y vo trng thi oxi ho cao
nht.
Vit (c gii thch) cng thc ca hp cht to thnh khi cho A tc dng vi
B.
*HD:
I
3
(X) v I
5
(Y) tng nhiu v t ngt.
Suy ra:
a. X thuc nhm II A, Y thuc nhm IV A trong bng HTTH cc nguyn t ho
hc.
b. A l XO, B l YO
2
.
112
c. Cc hp cht do A tc dng vi B: XYO
3
, X
2
YO
4
.
Bi 15
Thc nghim cho bit nng lng ion ho th nht (I
1
) v nng lng ion ho
th hai (I
2
) ca ba nguyn t sau (tnh ra kJ/mol):
Li Be B
I
1
: 520 899 801
I
2
: 7300 1757 2430
Hy gii thch v sao:
a) I
1
ca Be ln hn I
1
ca Li, B.
b) I
2
ca B nh hn I
2
ca Li nhng ln hn I
2
ca Be.
c) I
2
ca Be nh hn I
2
ca Li.
*HD:
Gii thch d kin thc nghim v nng lng ion ho. (kJ/mol).
Li
+
: 1s
2
Be
+
: 1s
2
2s
1

B
+
: 1S
2
2s
2

Trong nguyn t B do mc chn ca cc electron 1s
2
i vi electron 2s
khng hon ton nn Z
+
ca electron 2s trong B ln hn Z
+
ca electron 2s trong
I
2
(B) > I
2
(Be) do: phn lp 2s
1
ca Be
+
cha bo ho cn phn lp: 2s
2
ca B
+
bo ho. Hai electron trong cng phn lp 2s
2
do B
+
chn nhau yu, cn electron
2s
1
ca Be
+
b hai electron 1s
2
chn mnh.
I
2
ca Be nh hn I
2
ca Li v .
I
2
ca Be ng vi s tch electron khi phn lp 1s
2
bo ho, km bn.
113
I
2
ca Li ng vi s tch electron khi phn lp 1s
2
bo ho, bn vng.
Bi 16:
Electron lp ngoi cng ca nguyn t A ng vi 4 s lng t:
n = 4 ; l = 0 ; m = 0; s = +1/2.
a. Xc nh v tr ca A trong bng tun hon.
b. Cho bit tnh cht ha hc c trng ca A.Vit cu hnh electron sinh ra do
tnh cht c trung .
*HD:
a. Electron lp ngoi cng l 3d
1
.
*TH1: K (Chu k 4, phn nhm chnh nhm I).
*TH2: Cr: 3d
5
4s
1
(Chu k 4, phn nhm chnh nhm VI).
*TH3: Cu: 3d
10
4s
1
(Chu k 4, phn nhm ph nhm I).
b. K K
+
+ 1e Cu Cu
+
+ 1e
Cr Cr
3+
+ 3e Cu Cu
2+
+ 2e
Bi 17:
a. Nng lng ion ha I
1
ca mt s nguyn t thuc chu k 3:

Nguyn t Si P S Cl
I
1
786 1012 1000 1251
b. Nhit nng chy ca cc n cht thuc chu k 3:

n cht Na Mg Al Si P
114
t
0
n/c
(
0
C) 99 649 660 1410 44
Hy gii thch s bin i ?
*HD:
a.Trong mt chu k I
1
tng theo chiu tng ca s hiu nguyn t do lc ht gia
ht nhn nguyn t v e lp ngoi cng cng mnh. Tuy nhin trong mi chu k ta
thy c trng hp bt thng nh chu k 3: I
1(P)
> I
1(S)
.
Do : Cu hnh P: 3s
2
3p
3
.
Cu hnh S: 3s
2
3p
4
.
Trong nguyn t S,electron p th t cng chim 1obitan vi 1 electron p
khc,nn b y mnh hn nu ch c mt mnh n trong mt obitan.do e th t
d b tch ra khi nguyn t.Cu hnh ca electron p bn bo ha l p
3
kh bn
vng.
b.i t tri sang phi trong mt chu k t
0
n/c
cc n cht tng t cc kim loi n
kim v gim t ngt n phi kim.
*Gii thch: t
0
n/c
ca mt cht ph thuc vo hai yu t:
- Cu trc tinh th ca cht rn.
- Lin kt trong cht rn.
- Trong chu k 3: t
0
n/c
cc kim loi tng t Na Mg Al, tng t
ngt Si ri gim t ngt P: Do: + Si c cu trc tinh th nguyn t
+ P c cu trc tinh th phn t (P
4
).

Bi 18:
Nng lng cn thit tch 1electron ngoi cng ra khi nguyn t ca n
trng thi kh(hi) c gi l nng lng ion ha I
1
ca nguyn t (I
1
). Ngi ta o
115
c cc gi tr I
1
ca mt s nguyn t thuc cc chu k ngn trong bng tun
hon nh sau:
Nguyn t E F G H I J K L
in tch
ht nhn
Z Z + 1 Z +2 Z + 3 Z + 4 Z + 5 Z + 6 Z + 7
I
1
(KJ/mol) 1402 1314 1680 2080 495 738 518 786
- Nguyn t no thuc nhm kh tr.
- 8 nguyn t trn c thuc cng 1 chu k trong bng tun hon khng?
- Nguyn t no thuc kim loi kim,nguyn t no thuc halogen?
- Ti sao nguyn t J c gi tr I
1
cao hn nguyn t I v K trc v sau n?
- D on xem n cht L c t
0
n/c
cao hay thp? Ti sao?
*HD:
- 8 nguyn t c Z lin tc nhau, cc chu k nh mi nguyn t phi 1 nhm
chnh.Cc nguyn t thuc nhm kh him c cu trc e ngoi cng l bo ha (8e)
bn nn kh mt e Nng lng ion ha cao nht Nguyn t H.
- Nguyn t H c cu hnh ns
2
np
6
kt thc mt chu k nn 8 nguyn t trn thuc 2
chu k lin tip (khng cng 1 chu k)
- Kim loi kim l I,Halogen l G.
- J c cu hnh lp v ngoi cng l ns
2
,lp s bo ha nn kh bn nng lng
ion ha I
1
cao hn I(ns
1
v K(ns
2
np
1
) trc v sau n.
- L phi thuc nhm IVA,c 4e lp ngoi cng nn lin kt trong mng tinh th
(kiu kim cng) nn t
0
n/c
cao.
Bi 19:
Xt cc nguyn t: Cl ,S ,Mg ,Na ,Al ,P ,Si.Hy cho bit bn knh nguyn t,
m in,tnh kim loi ca cc nguyn t trn bin i ra saotheo chiu tng s hiu
nguyn t?gii thch?
116
*HD:
Cc nguyn t trn u thuc chu k 3 ca bng tun hoanftheo chiu tng ca Z:
Na , Mg , Al , Si , P , S , Cl.
- Bn knh nguyn t gim:Do nguyn t chng u c 3 lp e,khi Z lc ht tnh
in gia ht nhn v lp v tng lm bn knh nguyn t gim.
- m in tng: Do bn knh nguyn t gim lm cho e ngoi cng cng gn ht
nhn hn,b nhn ht vi lc ht mnh nn m in tng.
- Tnh kim loi gim: Do m in tng,s e ngoi cng tng nn kh nng
nhng e gim tnh kim loi gim.
Bi 20:
1.Chu k 7 nu s nguyn t th tng s nguyn t trong chu k l bao nhiu?
Gii thch.
2.Nguyn t 116 nu tm c s thuc chu k no? Nhm no? Gii thch?
3.Hy sp xp cc ion sau theo chiu r
nt
tng dn. Gii thch?
a. K
+
, Cl
-
, S
2-

b. Au
3+
, Au
+
.
4. Hy gi tn cc nguyn t v vit cc k hiu ha hc :
a. Nguyn t to thnh oxit baz nhm IIIA.
b. Nguyn t chuyn tip chu k 4 to ion 3+ m khng c e c thn.
c. Nguyn t chuyn tip chu k 4 to ion 2+ vi phn lp d bn bo ha.
d. Nguyn t chuyn tip chu k 5 to ion 3+ vi cu hnh e bn bo ha.
*HD:
117
1. Trong bng tun hon,mi chu k bt u l mt kim loi kim(ns
1
) v tn cng
l mt kh him(ns
2
np
6
).
Theo thi t mc nng lng ca cc obitan trong nguyn t ta c:
[
86
Rn]7s
2
6d
10
5f
14
7p
6
vy chu k 7 c 32 nguyn t.
2.z = 116 c cu hnh theo mc nng lng:
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
5d
10
5p
6
6s
2
4f
14
5d
10
6p
6
7s
2
5f
14
6d
10
7p
4
.
Vy nguyn t z = 116 thuc chu k 7,e c mc nng lng cao nht thuc obitan
p do thuc nhm VIA.
3.Sp xp theo chiu bn knh nguyn t tng dn.
a. K
+
< Cl
-
< S
2-
Do cc ion u c 18e(3 lp e) nhng in tch ht nhn ca cc
ion gim t K
+
> Cl
-
> S
2-
,lc ht tnh in gia ht nhn vi cc e tng nn bn
knh ion gim dn.
b. Au
3+
< Au
+
:Hai ion cng in tch ht nhn,nhng in tch Au
3+
> Au
+
nn
bn knh ion Au
3+
< Au
+

4. Gi tn
a.Nguyn t to oxit baz mnh nht nhm IIIA:
81
Tl (Thallium).
b.Nguyn t chuyn tip chu k 4 to 3+ m khng c e c thn l:
21
Sc(Scanium)
c.Nguyn t chuyn tip chu k 4 to ion 2+ vi phn lp d bn bo ha l:
25
Mn(Mangan).
d.Nguyn t chuyn tip chu k 5 to ion 3+ vi cu hnh e bn bo ha l:
39
Y(Ytrium).
Bi 21:
Cho 3 nguyn t c k hiu A, B, C cha bit,c c im:
118
- A,B,C c tng (n+l) bng nhau trong n
A
> n
B
, n
C
.
- Tng s e phn mc cui A,B bng tng s e phn mc cui ca C.A v C
ng k tip nhau trong bng tun hon.
- Tng i s 4 s lng t ca e cui cng ca C l 3,5.
a. Hy xc nh 4 s lng t ca e cui cng ca A,B,D.
b. Vit cu hnh e v cho bit v tr ca A, B, C trong bng tun hon.
c. Hy d on tnh cht ha hc c bn ca A, B, C.
*HD:
- A,B,C c tng (n+l) bng nhau trong n
A
> n
B
, n
C
v A, C ng k tip nhau
trong bng tun hon.Vy phn mc cui cng ca A ch c th l (n+l)s
1
v phn
mc cui cng ca C l np
6
.
-Theo bi tng i s 4 s lng t ca e cui cng ca C l: n + l + m + s = 3,5
(vi l=1,m=1,s=-1/2) n=2.
Vy phn mc cui cng ca C l 2p
6
,ca A l 3s
1
.
- Gi x l s e ca phn mc cui ca B, ta c:
1+ x = 6 x = 5 Phn mc nng lng cui ca B l: 2p
5
.
a. B 4 s lng t ca A, B, C l:
A: n=3,l=0,m=0,s=+1/2
B: n=2,l=1,m=0,s=-1/2
C: n=2,l=1,m=+1,s=-1/2
b.Vit cu hnh e v v tr ca A, B, C trong bng tun hon :
A: 3s
1
STT 11,chu k 3,nhm IA Kim loi kim c tnh kh mnh.
119
B: 2p
5
STT 9, chu k 2, nhm VIIA Phi kim in hnh c tnh oxihoa
mnh.
C: 2p
6
STT 10, chu k 3, nhm VIIIA Kh him, tr v mt ha hc.
Bi 22:
Hai nguyn t A, B c cu hnh e cui cng ng vi 4 s lng t:
A: n=3,l=2,m=-2,s=-1/2
B: n=3,l=1,m=-1,s=-1/2
a.Vit cu hnh e ca A v B v cc ion m A,B c th to thnh.
b. Xc nh v tr ca A,B trong bng tun hon.Gii thch.
c. A,B to c bao nhiu oxit v hiroxit. Vit CTPT ca chng.i vi mi
nguyn t hy so snh tnh axit,baz ca cc hiroxit.gii thch.

*HD:
a. A: 3d
6
4s
2
A
2+
: 3d
6
A
3+
: 3d
5
A l : Fe
B: 4p
4
B
2-
: 4p
6
B l : S
b. A B
Oxit FeO, Fe
2
O
3
, Fe
3
O
4
SO
2
, SO
3

Hiroxit Fe(OH)
2
, Fe(OH)
3
H
2
SO
3
, H
2
SO
4

c. Tnh baz ca: Fe(OH)
2
> Fe(OH)
3

Tnh baz ca: H
2
SO
3
< H
2
SO
4

Bi 23:
120
1. Bng tun hon Meneleep ra i nm 1871 c nhng nh hng c ngha to
ln. l nhng nh hng g?
2. Cho 2 nguyn t A, B ng k tip nhau trong bng tun hon(n+l) bng nhau.
Trong s lng t chnh ca A ln hn s lng t chnh ca B. Tng i s
ca b 4 s lng t ca e cui cng ca B l 4, 5.
a. Xc nh b 4 s lng t ca e cui cng trn A,B.
b. Vit cu hnh e ca v suy ra v tr ca A, B trong bng tun hon.
*HD:
1. Bng tun hon c nhng nh hng nh sau:
- nh hng cho vic pht hin ra nhng nguyn t mi.
- Hiu nh nhiu khi lng nguyn t xc nh cha chnh xc trc .
- D on nhiu tnh cht l ha hc.
2.
A: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1

B: 1s
2
2s
2
2p
6
3s
2
3p
6

Bi 24:
Tng s cc loi ht p, n, e trong nguyn t nguyn t A l 108.hy:
- Cho bit A thuc chu k my trong bng tun hon.
- Bit A nhm V, xc nh v tr A trong bng tun hon.
- Tnh % theo khi lng ca A trong oxit cao nht.
*HD:
Ta c : 2Z + N=108 v 1 N/Z 1,5 30,6 Z < 36 : Z= 31 35.
121
Nhn thy vi cu hnh: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2

th nguyn t c Z=30.Vy nguyn
t A c Z= 31 35

thuc chy k 4.
- Khi A thuc nhm V c 5e lp ngoi cng cu hnh 3d
10
4s
2
4p
3

Z
A
= 33 A l As: s 33,chu k 4,nhm VA.
A
As
= 33+(108-2.33)=75
Oxit cao nht: As
2
O
5
:%m
As
trong As
2
O
5
l: 75.2.100/(75.2+16.5)=65,22%.
Bi 25:
X thuc chu k 4,Y thuc chu k 2 ca bng tun hon.I
i
l nng lng ion
ha th i ca mt nguyn t,thc nghim cho bit t s I
k+1
/I
k
ca X v Y nh sau:

I
k+1
/I
k
I
2
/I
1
I
3
/I
2
I
4
/I
3
I
5
/I
4
I
6
/I
5

X 1,94 4,31 1,31 1,26 1,30
Y 2,17 1,96 1,35 6,08 1,25
Lp lun xc nh X v Y.
*HD:
i vi X t I
2
n I
3
tng t ngt do ion X
2+
c cu hnh e ca kh him
[Ar]4s
2
X l: Ca.
i vi Y t I
4
n I
5
tng t ngt,ion Y
4+
c cu hnh e ca kh him nn cu
hnh Y l [He]2s
2
2p
2
nn Y l: C.
Bi 26:
Cho bit tr s nng lng ion ha th nht I
1
(eV) ca cc nguyn t chu k 2:

122
Nguyn t Li Be B C N O F Ne
I
1
(eV) 5,39 9,3 8,29 11,26 14,54 13,61 17,41 21,55
Nhn xt s bin thin nng lng ion ha th nht I
1
(eV) ca cc nguyn t trn.
Gii thch.
*HD:
Nhn xt:Nhn chung nng lng ion ha th nht I
1
(eV) ca cc nguyn t tng
dn t tri qua phi.
Gii thch:
- Trong mt chu k, nguyn t ca cc nguyn t c s lp e bng nhau. T tri
qua phi in tch ht nhn tng,ng thi s e lp ngoi cng tawngleen, bn knh
nguyn t gim dn. V vy, nng lng tch e ra khi nguyn t cng ln.
- Ring Be v N c nng lng ion ha cao bt thng:
+ Be c cu hnh 1s
2
2s
2
cc phn lp s bo ha, y l cu hnh bn.
+ N c cu hnh 1s
2
2s
2
2p
3
phn lp s bo ha, phn lp p bn bo ha cng l
cu hnh bn nn cn cung cp nng lng cao hn ph v cu hnh ny.
Bi 27:
1. i lc e ca mt nguyn t l g? N ph thuc vo nhng yu t no?
2. v sao i lc e th nht thng l dng, cn i lc e th hai lun m?
3. gii thch s bin i i lc e ca cp sau
Nguyn t C N
i lc(eV) 1,24 0,27
4. Gii thch v sao F l phi kim mnh hn Cl nhng i lc e ca n 3,58(eV) li
nh hn ca Clo 3,81(eV).
123
*HD:
1.
- i lc e ca mt nguyn t l nng lng qu trnh nguyn t ca nguyn t (
trng thi kh)kt hp thm 1e to thnh ion m.
- i lc e ca mt nguyn t ph thuc vo nhng yu t sau:Bn knh nguyn
t,tc dng chn ca e gia ht nhn v cc e thm vo,s sp xp e vo cc obitan
c nng lng cao hn hoc cc obitan bn bo ha.
2. Tc dng chn v s lng e ca i lc e th nht t hn i lc e th 2 gia ht
nhn nguyn t v e thm vo,nn i lc e th nht c nng lng ht ln hn nng
lng y nn i lc e th nht thng l dng,cn i lc e th hai lun m.
3. C c cu hnh 1s
2
2s
2
2p
2
;N c cu hnh 1s
2
2s
2
2p
3

C: Nhn thm 1e t cu hnh bn bo ha nn i lc th nht dng.
N: t cu hnh bn bo ha,nu nhn thm 1e li t cu hnh khng bn do
i lc e th nht m.
4. Do bn knh nguyn t F nh hn Cl nn chu tc dng chn mnh hn ca cc e
c sn,do i lc e ca F nh hn Cl
Bi 28:
3 nguyn t X,Y,Z cng mt chu k,c tng s hiu nguyn t l 39.S hiu
nguyn t ca Y bng trung bnh cng s hiu nguyn t ca X v Z. Nguyn t
ca 3 nguyn t trn hu nh khng phn ng vi nc nhit thng.
- Vit cu hnh e nguyn t ca cc nguyn t v gi tn tng nguyn t.
- So snh m in,bn knh nguyn t ca cc nguyn t .
- So snh tnh baz ca cc hiroxit ca cc nguyn t .
*HD:
124
Gi x, y, z l s hiu nguyn t tng ng ca X, Y, Z.
Ta c x+y+z = 39 x+z=26 X, Y, Z cng thuc chu k 3.
2y=x+z
y=13 v X, Y, Z cng thuc chu k 3 Nghim ph hp x=12, y=14.
Tn 3 nguyn t : Mg , Al , Si
+ Th t m in : Mg < Al < Si
+ Th t bn knh nguyn t: Mg > Al > Si
+ Th t tnh baz: Mg(OH)
2
> Al(OH)
3
> H
2
SiO
3
.















125
Chuyn 5
TNH pH TRONG DUNG DCH

T Ha Sinh, trng THPT chuyn Lo Cai

I. Cc nh lut c bn ca ho hc p dng cho h cc cht in li:
1. nh lut hp thc:
nh gi bn nh lng chiu hng v mc xy ra ca cc phn ng cn
da vo i lng hng s cn bng. V nguyn tc hng s cn bng ca phn
ng cng ln th phn ng xy ra theo chiu thun cng mnh.
a. To phn ng: L t l gia bin i s mol (nng ) vi h s hp thc
ca cu t tng ng.
Xt phn ng:
... ....
3 3 2 2 1 1
+ + + + + +
t t q q p p
A A A A A A

i
i
C
x hoac

=
i
i
n


i i i
x n . C ; .
i
= =
n (C) cng ln khi to cng ln. Nh vy to phn ng c trng cho
mc hon ton ca phn ng.
n (C) < 0 i vi cc cht u v n (C) > 0 i vi cc cht to thnh sau
phn ng.

i
< 0 vi cht u v
i
> 0 vi cht to thnh sau phn ng.
VD: Xt phn ng
Fe
3
O
4 (r)
+ 4CO
(k)
3Fe
(r)
+ 4CO
2

126
T 0,2 mol Fe
3
O
4
v 0,5 mol CO to ra c 0,3 mol Fe
Hy xc nh thnh phn ca hn hp sau phn ng?


Fe
3
O
4 (r)
+ 4CO
(k)
3Fe
(r)
+ 4CO
2

H/s hp thc : -1 - 4 3 4
S mol ban u: 0,2 0,5 0 0
S mol sau p/ 0,1 0,1 0,3 0,4
bin i s mol -0,1 -0,4 0,3 0,4
To phn ng: = 0,3/3 = 0,1 (tnh i vi Fe)
bin i s mol:
nCO
2
= 0,1. 4 = 0,4
nCO = 0,1. (-4) = -0,4
n Fe
3
O
4
= 0,1 . (-1) = -0,1
S mol sau phn ng:
nCO
2
= 0,4 ; nCO= 0,5 0,4 = 0,1;
nFe
3
O
4
= 0,2 0,1 = 0,1; nFe = 0,3
b. To cc i: (p dng cho cht tham gia phn ng)

i
i i
i
i
C C C
x


=

=
x t x
max
khi C
i
0

i
i
C
x

=
127
To cc i ca phn ng: Gi tr nh nht trong s c to cc i ca
phn ng

<

<

= 0 , min ; 0 , min
0
max
0
max i
i
i
i
i
i
n C
x


iu c ngha l phn ng xy ra cho n trit tiu hon ton nng ca cu
t c gi tr
i
i
C

= min.
VD1: Xt hn hp gm
Fe
2+
0,3M; Cr
2
O
7
2-
0,01 M; H
+
0,07M
6Fe
2+
+ Cr
2
O
7
2-
+ 14H
+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O (1)

i
-6 -1 -14 6 2 7
0
i
C 0,3 0,01 0,07 0 0 0
x
max
( Fe
2+
) = 0,05
x
max
(Cr
2
O
7
2-
) = 01 , 0
1
01 , 0
=


min 005 , 0
14
07 , 0
) (
max
=

=
+
H x
x
max
ca phn ng = x
max
(H
+
) = 0,005
- Trong trng hp tng qut xc nh to cc i ca phn ng ta ly nng
cu tng cht u
0
i
C (hoc s mol ban u
0
i
n ) chia cho h s hp thc tng
ng
i
v chn gi tr nh nht.
c. Thnh phn gii hn (TPGH): l thnh phn ca h sau khi phn ng xy ra
vi to cc i
Vi VD1: Thnh phn gii hn l thnh phn sau khi phn ng (1) xy ra vi to
x= 0,005
128
6Fe
2+
+ Cr
2
O
7
2-
+ 14H
+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O (1)

i
-6 -1 -14 6 2 7
0
i
C 0,3 0,01 0,07 0 0 0
i
C -0,03 -0,005 -0,07 0,03 0,01
i
C 0,27 0,005 0 0,03 0,01
TPGH: Fe
2+
= 0,27 M; Cr
2
O
7
2-
= 0,005M; Cr
3+
= 0,01M; Fe
3+
= 0,03M
Nu h c nhiu phn ng xy ta ln lt th thnh phn gii hn l thnh
phn sau khi phn ng cui cng xy ra vi to cc i.
VD2: Xc nh thnh phn gii hn ca dung dch gm (NH
4
)
3
PO
4
0,1M v HNO
3

0,25M
HNO
3
; (NH
4
)
3
PO
4
l nhng cht in li mnh phn li hon ton.
HNO
3
H
+
+ NO
3
-

0,25 0,25
(NH
4
)
3
PO
4
3NH
4
+
+ PO
4
3-

0,3 0,1
Phn ng xy ra ln lt
1. PO
4
3-


+ H
+
HPO
4
2-

C
0
0,1 0,25
C - 0,15 0,1
C - 0,1 -0,1 0,1
2. H
+
+ HPO
4
2-
H
2
PO
4
-

C
0
0,15 0,1
C 0,05 - 0,1
129
C - 0,1 - 0,1 0,1
3. H
2
PO
4
-
+ H
+
H
3
PO
4

C
0
0,1 0,05
C 0,05 -- 0,05
C - 0,05 - 0,05

TPGH: H
3
PO
4
: 0,05M + H
2
PO
4
2-
0,05M + NH
4
+
: 0,3M + NO
3
-
: 0,25M
TPGH c th trng vi thnh phn cn bng nu sau phn ng khng c
mt qu trnh no xy ra lm thay i nng ca cc cu t trong TPGH.
Trong a s trng hp th cc cu t xc nh c t TPGH s tham gia vo cc
qu trnh ph dn ti s thit lp mt thnh phn cn bng khc vi thnh phn
gii hn.
Trong VD 2 cc qu trnh xy ra l:
NH
4
+
NH
3
+ H
+

H
3
PO
4
H
2
PO
4
-
+ H
+

H
2
PO
4
-
HPO
4
2-
+ H
+

HPO
4
2-
PO
4
3-
+ H
+

Lm cho TPGH khc vi thnh phn cn bng.
2. nh lut bo ton nng ban u:
a. Biu din nng trong tnh ton cn bng:
C
o
: nng gc ( nng cc cht trc khi a vo hn hp phn ng).
C
o
: nng ban u (nng c cht sau khi a vo hn hp phn ng nhng
cha tham gia phn ng).
| | : nng cc cht trng thi cn bng.
130
VD: Trn 10 ml dung dch HNO
3
0,02M vi 40ml dung dch NaOH 0,1M. Xc
nh C
o
; C
o
, | | ca cc cu t?
C
o
HNO
3
= 0,02M; C
o
NaOH = 0,1 M
C
o
HNO
3
= M 004 , 0
50
10 . 02 , 0
= ; C
o
NaOH = M 08 , 0
50
40 . 1 , 0
=

Phn ng: HNO
3
+ NaOH NaNO
3
+ H
2
O
C
o
0,004 0,08
C --- 0,076 0,004
TPGH ca h: NaOH: 0,076 M; NaNO
3
: 0,004M
NaOH Na
+
+ OH
-

0,076 0,076 0,076 M
NaNO
3
Na
+
+ NO
3
-

0,004 0,004 0,004 M
Cn bng : H
2
O H
+
+ OH
-
K
w
= 10
-14
<< b qua
| | | | | | M NO M OH M Na 04 , 0 ; 076 , 0 ; 08 , 0
3
= = =
+

b. nh lut bo ton nng ban u: Nng ban u ca 1 cu t bng tng
nng cn bng cu tt c cc dng tn ti ca cu t .
Trong trng hp cu t ban u l n nhn nhng trng thi cn bng
li tn ti dng kin hp th trong biu thc nh lut bo tan nng ban
u phi k n h s hp thc ca cu t trong phn t lin hp.
VD1: Vit biu thc nh lut bo ton nng i vi cc cu t trong dd CdCl
2

0,01M. Bit rng trong dung dch c cc cn bng sau:
CdCl
2
Cd
2+
+ 2Cl
-

131
Cd
2+
+ Cl
-
CdCl
+

CdCl
+
+ Cl
-
CdCl
2
(phc)
CdCl
2
+ Cl
-
CdCl
3
-

CdCl
3
-
+ Cl
-
CdCl
4
2-

Cd
2+
+ H
2
O Cd (OH)
+
+ H
+

2Cd
2+
+ H
2
O Cd
2
(OH)
3+
+ H
+

H
2
O H
+
+ OH
-

| |
(

+
+
(

+
+
(


+
(


+ +
(

+
+
(

+
= =
+
3
2
2
2
4 3 2
2
01 , 0
2
OH Cd CdOH
CdCl CdCl CdCl CdCl Cd C
Cd

C
Cl
-

= 0,02 = |Cl
-
| + |CdCl
+
| + 2 |CdCl
2
| + 3|CdCl
3
-
| + 4|CdCl
4
3-
|
3. nh lut bo ton in tch:
Tng in tch m ca cc anion = tng in tch dng ca cc cation.
in tch ca mi ion = |i|. in tch tng ng ca ion .
p dng nh lut bo ton in tch cho VD trn:
2 |Cd
2+
| + |CdCl
+
| + |CdOH
+
| + 3|Cd
2
OH
3+
| + |H
+
|
= |Cl
-
| + |CdCl
3
| + 2|CdCl
4
2-
| + |OH
-
|.
4. nh lut bo ton proton (iu kin proton - KP)
Nu chn mt trng thi no ca dung dch ( c th l trng thi ban u
hoc mt trng thi gi nh no ) lm trng thi so snh m ta gi l mc khng
th nng proton ca dung dch trng thi cn bng bng tng nng proton
do cc cht t mc khng phn li ra tr tng nng proton b cc cht mc
khng thu vo t ti trng thi cn bng .
| | | | ( ) | | ( )
vao thu
i
phong giai
i
H H H


+ + +
=
132
VD
1
: Vit biu thc DKP cho dd HCN nng C (M)
HCN H
+
+ CN
-

H
2
O H
+
+ OH
-

Chn MK: HCN; H
2
O
KP: | | | | | | | | | |
+ + +
+ = + = OH CN H H H
2 1

Nu chn MK l CN
-
; H
2
O:
H
2
O H
+
+ OH
-

CN
-
+ H
2
O HCN + OH
-

( CN
-
+ H
+
HCN)
KP: |H
+
| = |OH
-
| - |HCN|
nh lut bo ton nng u:
C
HCN
= |HCN| + |CN
-
|
|HCN| = C - |CN
-
|
VD
2
: Vit biu thc KP i vi dd CH
3
COOH (C
1
M) v CH
3
COONa (C
2
M)
CH
3
COOH CH
3
COO
-
+ H
+
(1)
H
2
O H
+
+ OH
-
(2)
CH
3
COO
-
+ H
+
CH
3
COOH (3)
H lin hp ch chn 1 cht lm mc khng

Chn MK: CH
3
COOH ; H
2
O
|H
+
| = |CH
3
COO
-
| - C
2
+ |OH
-
|
Nu chn MK l: CH
3
COONa ; H
2
O
133
|H
+
| = |OH
-
| - ( |CH
3
COOH| - C
1
)
= |OH
-
| - |CH
3
COOH| + C
1

VD
3
: Vit biu thc DKP cho dd H
3
PO
4




MK: H
3
PO
4
; H
2
O
H
3
PO
4
H
+
+ H
2
PO
4
-

H
3
PO
4
2H
+
+ HPO
4
2-

H
3
PO
4
3H
+
+ PO
4
3-

H
2
O H
+
+ OH
-

KP:
|H
+
| = | H
2
PO
4
-
| + 2| HPO
4
2-
| +3| PO
4
3-
| +| OH
-
|
Nu chn MK l: HPO
4
-
; H
2
O
HPO
4
2-
H
+
+ PO
4
3-

H
2
O H
+
+ OH
-

HPO
4
2-
+ H
+
H
2
PO
4
-

HPO
4
2-
+ 2H
+
H
3
PO
4

KP:
|H
+
| = | PO
4
3-
| + | OH
-
| - | H
2
PO
4
-
| - 2| H
3
PO
4
|
5. nh lut tc dng khi lng :
a A + b B c C + d D K: hng s cn bng nhit ng
Chn mc khng l cu t no ch vit phng trnh cho nhn proton t cu t
134

( ) ( )
( ) ( )
b a
d c
B A
D C
K
.
.
=

Quy c:
- Hot cht rn v cht lng nguyn cht c coi bng 1
- Hot cht kh nm cn bng vi dung dch bng p sut ring phn
- i vi dung dch rt long a = C
II. Tnh cn bng theo nh lut tc dng khi lng:
+ Chn n s:
K rt b: Chn n s l nng cc cht to thnh sau phn ng, y n s
thng l to phn ng.
K rt ln: Chn n s l nng cc cht u, nn chn cht ng vi to
phn ng cc i.
T n s chn tnh ra to phn ng v suy ra nng cn bng ca cc
cu t khc
VD: nh gi kh nng ho tan ca AgI trong NH
3
1,0M
Bit c cc cn bng sau:

AgI Ag
+
+ I
-
K
s2
= 10
-16

Ag
+
+ 2 NH
3
Ag(NH
3
)
2
+
= 10
7,24

AgI + 2NH
3
Ag(NH
3
)
2
+
+ I
-
K
2

K
2
= K
s2
. = 10
-16
. 10
7,24
= 10
-8,76


K b d on AgI kh tan trong NH
3

135
nh gi nh lng cn tnh tan ca AgI trong NH
3
.
K b t n v phi ca phng trnh. t to phn ng l x:

AgI + 2NH
3
Ag(NH
3
)
2
+
+ I
-
10
-8,76

C 1
C -2x x x
| | 1 - 2x x x
nh lut tc dng khi lng:

( )
( )
38 , 4
38 , 4 76 , 8
2
2
10 x 1 2x be
10
2 1
10
2 1


= <<
=

K
x
x
x
x

Vy tan S ca AgI trong NH
3
l :
S = |Ag(NH
3
)
2
+
| = |I
-
| = 10
-4,38
= 4,2 . 10
-5
M
Vy c th coi AgI tan khng ng k trong NH
3


MT S DNG BI TP V TNH pH TRONG DUNG DCH

Nguyn tc chung trong tnh ton cn bng:
- M t trng thi ban u ca dung dch.
- Xt cc tng tc ho hc Xc nh thnh phn gii hn (TPGH).
- M t cc cn bng (tnh ton cc hng s cn bng nu cn). So snh cc
hng s cn bng rt ra cn bng ch yu (b qua cc cn bng khng ng k
so vi cn bng chnh) nh gi bn nh lng bn cht ca phn ng trong
dung dch
136
- lut tc dng khi lng + lut bo ton vt cht khc thit lp cc
phng trnh lin h.
Tnh pH ca dung dch axit, baz, mui v dung dch m:
( Cn bng axit - baz )
Lu chn cu t c nng t thay i nht hoc nng ln nht lm
mc khng php lp trong qa trnh tnh l nh nht

1. Tnh pH cho dung dch axit mnh, baz mnh:
dd axit mnh HY nng C
A
(M)
HY H
+
+ Y
-

H
2
O H
+
+ OH
-

MK: HY; H
2
O
KP: |H
+
| = |OH
-
| + |Y
-
| =
| |
A
C
H
K
w
+
+

- C 10
-6
M |H
+
| = |Y
-
| = C
A


- C 10
-6
M Gii phng trnh bc 2
VD: Tnh pH ca dd HNO
3
1.10
-3
M
C
1
: So snh cc cn bng rt ra cn bng ch yu trong dd
C
2
: Tnh theo nh lut tc dng khi lng
C
3
: p dng nh lut bo ton proton
dd baz mnh XOH nng C
B
(M)
XOH X
+
+ OH
-

pH = - lg CA
137
H
2
O H
+
+ OH
-

Tng t cho trng hp dd axit mnh


2. Tnh pH cho dung dch n axit yu, n baz yu:
dd n axit yu HA nng C
A
:
HA H
+
+ A
-
K
a

(1)
H
2
O H
+
+ OH
-
K
w
(2)






MK: HA; H
2
O
KP: |H
+
| = |OH
-
| + |A
-
| =
| |
| |
| |
+ +
+
H
HA K
H
K
a w
.

Bi 1: Tnh pH ca dung dch
a/ CH
3
COOH 0,1 M bit pK
a
= 4,75
b/ NH
4
Cl 0,1M bit NH
3
c pK
b
= 4,75
Gii
a/ CH
3
COOH CH
3
COO
-
+ H
+
K
a
= 10
-4,75

H
2
O H
+
+ OH
-
K
w
= 10
-14

pH = pKw + lg CB
So snh cn bng (1) v (2)
+ K
a
.C
A
>> K
w
: b qua s phn li ca H
2
O Tnh cn bng theo lt/d khi lng cho (1)
+ K
a
.C
A
K
w
: Thit lp iu kin proton tnh ton.
138
C K
a
. C
CH3COOH
>> K
w
Cn bng (1) l ch yu.
p dng /l tc dng khi lng cho cn bng (1)
h = C Ka. = 1,33 .10
-3
(M) pH = 2,87
b/ Tng t:
pH = 5,13
Bi 2: Tnh pH ca dung dch HCN nng 10
-4
(M). Bit pK
a
= 9,35
Gii:
HCN H
+
+ CN
-

H
2
O H
+
+ OH
-

C K
a
. C
a
K
w
Cn bng (1) v (2) l tng ng Tnh ton theo kproton
Chn MK: HCN; H
2
O
KP: | | | | | | | | | |
+ + +
+ = + = OH CN H H H
2 1


| |
| |
| | | |
| |
| | HCN K K h
HCN K K h
H
K
H
HCN K
H
a w
a w
w a
+ =
+ =
+ =
+ +
+
2
.

Chp nhn gn ng |HCN|
0
= C
a
= 10
-4
(M) h = 10
-6,36
pH = 6,36
Dung dch n baz yu NaA nng C
B
(M): Tng t dung dch n
axit yu.
H
2
O H
+
+ OH
-
K
w
A
-
+ H
2
O HA + OH
-
K
b




So snh cn bng (1) v (2)
+ K
b
.C
A
>> K
w
: b qua s phn li ca H
2
O Tnh cn bng theo lt/d khi lng cho (1)
+ K
b
.C
A
K
w
: Thit lp iu kin proton tnh ton tng t n axit.
139



Hn hp cc n axit v n baz:
a. Hn hp n axit mnh v axit yu:
Bi 3: Tnh pH ca dung dch thu c khi trn 40 mol HCl 2,5.10
-2
(M) vi 60ml
CH
3
COOH 1,667. 10
-4
(M)
Gii:
Cch 1:
C
HCl
= 10
-2
(M) ; C
CH3COOH
= 1,667.10
-4
.0,6 = 10
-4
(M)
HCl H
+
+ Cl
-
(1)
CH
3
COOH CH
3
COO
-
+ H
+
K
a
= 10
-4,76
(2)
H
2
O H
+
+ OH
-
K
w
= 10
-14
(3)
K
a
C
2
= 10
-8,76
>> 10
-14
Cn bng (2) l ch yu
CH
3
COOH CH
3
COO
-
+ H
+
K
a
= 10
-4,76

10
-4
10
-2

10
-4
x x 10
-2
+ x
p dng l tc dng khi lng:

( )
76 , 4
4
2
10
10
10

+
=
x
x x
K
a

x
2
+ (10
-2
+ 10
-4,76
) x 10
-8,76
= 0 x = 1,74.10
-7

h = 10
-2
+ 1,74.10
-7
10
-2

Cch 2:
140
MK : CH
3
COOH, H
2
O; HCl.
KP:
|H
+
| = |CH
3
COO
-
| + C + |OH
-
|
h =
| |
h
COOH CH K
a 3
.
+ C +
h
K
w
h
2
- C
HCl
. h ( K
a
. C
CH3COOH
+ K
W
) = 0
K
a
. C
CH3COOH
>> K
W
h
2
- 10
-2
h 10
-8,76
= 0 h 0,01 M pH 2
b. Hn hp cu baz mnh v baz yu:
Bi 4: Trn 20ml dd NaOH 3.10
-2
M vi 10ml NH
4
Cl 1,5.10
-2
M. Tnh pH ca dd
thu c?
Gii:
C NaOH = 2.10
-2
(M); C NH
4
Cl = 5.10
-3
(M)
NaOH + NH
4
Cl NH
3
+ H
2
O + NaCl
C 2.10
-2
5.10
-3
(M)
| | 1,5.10
-2
0 5.10
-3
(M)
Thnh phn gii hn ca h:
NaOH : 1,5.10
-2
M;
NH
3
: 5.10
-3
M
Cn bng trong dung dch:
NaOH Na
+
+ OH
-

1,5.10
-2
1,5.10
-2

NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= K
w
. K
a
-1
= 10
-4,76

H
2
O H
+
+ OH
-
K
w
= 10
-14

Ta c K
b
.C = 10
-4,76
. 5.10
-3
= 5.10
-7,76
>> K
w
b qua cn bng phn li ca H
2
O
Tnh theo cn bng ca NH
3
.
141
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 10
-4,76

C 5.10
-3
1,5.10
-2

| | 5.10
-3
x x 1,5.10
-2
+ x
nh lut tc dng khi lng:

( )
= =

+
=

x
x
x x
K
b
76 , 4
3
2
10
10 . 5
10 . 5 , 1
| OH
-
| = pH =
c. Hn hp n axit:
HA
1
: C
1
, K
a1
; HA
2
: C
2
, K
a2
; HA
3
: C
3
, K
a3
.
K
a
no ln vit cn bng trc:
HA
1
H
+
+ A
1
-
(1) K
a1

HA
2
H
+
+ A
2
-
(2) K
a2

.
HA
n
H
+
+ A
n
-
(n) K
an

H
2
O H
+
+ OH
-
(n+1) K
w
= 10
-14








Bi 5: Tnh nng cc ion c trong dd gm : HSO
4
-
: 0,01M, pK
a1
= 2;
HCN : 0,1M, pK
a2
= 9,35 ; HClO 0,10M, pK
a3
= 7,53
* So snh:
+ Nu C
1
= C
2
= C
3
= C
n
so snh cc K
ai

+ Nu C
1
C
2
. C
n
:
- nu K
a1
C
1
>> K
a2
C
2
> K
a3
C
3
> > K
an
C
n
(a) coi cn bng

(1) l ch yu tnh theo
nh lut tc dng khi lng cho cn bng (1)
- Nu kin (a) khng tho mn th tnh theo KP vi iu kin gn ng lin tc.
142
Gii:
HSO
4
-
H
+
+ SO
4
2-
K
a1
= 10
-2

HClO H
+
+ ClO
-
K
a3
= 10
-7,53

HCN H
+
+ CN
-
K
a2
= 10
-9,75

H
2
O H
+
+ OH
-
K
w
= 10
-14

Ta c Ka
1
.C
1
= 10
-4
>> K
a2
.C
2
= 10
-8,53
> K
a3
.C
3
= 10
-10,35
> K
w

Trong dd cn bng (1) l ch yu
HSO
4
-
H
+
+ SO
4
2-
K
a1
= 10
-2

C 0,01
| | 0,01 h h h
| | | |
+
= = = =

2
4
3 2
2
) ( 10 . 18 , 6 10
01 , 0
SO H M h
h
h

Kim tra iu kin:
| | | |
| | | |

<< =
+
=
+
=
<< =
+
=
+
=
2
4
10
3 35 , 9
35 , 9
3
3
3
2
4
7
3 35 , 7
35 , 7
2
2
2
10 . 22 , 7
10 . 18 , 6 10
10
. 01 , 0 .
) ( 10 . 17 , 4
10 . 18 , 6 10
10
. 1 , 0 .
SO
h K
K
C CN
SO M
h K
K
C ClO
a
a
a
a

Bi 6: Tnh pH ca dung dch C
6
H
5
COOH 0,02M, pK
a2
= 4,2 ; HCOOH: 0,05M
pK
a1
= 3,75
Gii:
HCOOH H
+
+ HCOO
-
K
a1
= 10
-3,75
(1)
C
6
H
5
COOH H
+
+ C
6
H
5
COO
-
K
a2
= 10
-4,2
(2)
H
2
O H
+
+ OH
-
K
w
= 10
-14
(3)
So snh:
143
K
a1
.C
1
= 5.10
-5,75
K
a2
.C
2
= 2.10
-6,2
>> K
w
= 10
-14

Chn MK: HCOOH; C
6
H
5
COOH; H
2
O
KP:
| | | | | | | |
| |
| | | |
h
COOH H C K
h
HCOOH K
h
K
H h
COO H C HCOO OH H
a a w 5 6 2 1
5 6
+ + = =
+ + =
+
+

| | | | COOH H C K HCOOH K K h
a a w 5 6 2 1
. . + + = (4)
Gn ng bc 1: Chp nhn | |
i
C i = th vo (4)
h
1
= 10
-2,496
= 3,186.10
-3
(M)
Kim tra li iu kin gn ng

| |
| | 0196 , 0 .
0475 , 0 .
1 2
1
2 1 5 6
1 1
1
1 1
=
+
=
=
+
=
h C
h
C COOH H C
h C
h
C HCOOH

Gn ng bc 2:
) ( 10 . 112 , 3 10 . 0196 , 0 10 . 0475 , 0 10
3 2 , 4 75 , 3 14
2
M h

= + + =
Kim tra li iu kin gn ng
| | | |
1 2
0473 . 0 HCOOH HCOOH =
| | | |
1 5 6 2 5 6
0196 . 0 COOH H C COOH H C = =
Vy kt qu lp:
pH = - lg (3,112.10
-3
) = 2,507
d. Hn hp cc n baz: tng t hn hp cc n axit thay K
a
bng K
b

e. Hn hp cc axit v baz lin hp:
HA: C
a
; A
-
: C
b
K
a

144
Trong dd c cc cn bng:
HA H
+
+ A
-
K
a
(1)
H
+
+ A
-
HA K
a
-1
(2)
H
2
O H
+
+ OH
-
K
w
= 10
-14
(3)
+ KP
+ MK: HA; H
2
O
| | | | | |
b
C A OH H h + = =
+


| |
b
a w
C
h
HA K
h
K
h + =
.

h
2
+ C
b
.h (K
w
+ K
a
. | | HA ) = 0 (4)
T (4) nu:
| |
| |
a a a b
a w
b
C K HA K hC
HA K K
C h
. .
.
=

<<
<<

) 5 ( .
b
a
a
C
C
K h =






Bi 7: Tnh nng cc ion trong h gm: NH
4
Cl: 0,02M; NH
3
: 0,04M
Gii:
Tnh pH gn ng:
pH = - pK
a
+ lg C
b
lg C
a

Nu:
b
a
a
C
C
K h . = > 10
-7
mi trng axit tnh theo (1)
< 10
-7
: mi trng baz Tnh theo (2)
10
-7
: Tnh theo iu kin proton
145
b
a
a
C
C
K h . = = 10
-9,24
.
04 , 0
02 , 0
<< 10
-7
Mi trng baz tnh theo cn bng baz
NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
= 10
-4,76

C 0,04 0,02
| | 0,04 x 0,02 + x x
K
b
=
( )
76 , 4
10
04 , 0
02 , 0

=

+
x
x x

x = 3,47.10
-5
(M) pOH = 4,46 pH = 9,54
f. Hn hp n axit yu v n baz yu bt k:
Bi 8: Tnh pH ca dung dch CH
3
COONH
4
0,01M
Gii:
CH
3
COONH
4
CH
3
COO
-
+ NH
4
+

0,01 0,01 (M)
NH
4
+
NH
3
+ H
+
K
a1
= 10
-9,24

H
2
O H
+
+ OH
-
K
w
= 10
-14

CH
3
COO
-
+ H
+
CH
3
COOH K
a2
-1
= 10
4,76

KP:

| | | | | | | |
| |
| |

+
+
+
+
=
+ = =
COO CH K
NH K K
h
COOH CH NH OH H h
a
a w
3
1
2
4 1
3 3
. 1

Gn ng bc 1: Chp nhn | |
i
C i =
h
1
= =
+
+

01 , 0 . 10 1
01 , 0 . 10 10
76 , 4
24 , 9 14

3. Dung dch a axit, a baz:
146
H
n
A : C ; K
ai

H
n
A H
n-1
A
-
+ H
+
K
a1

H
n-1
A
-
H
n-2
A
2-
+ H
+
K
a2

.
HA
n-1
A
n-
+ H
+
K
an





Bi 9: Tnh cn bng trong dd H
2
C
2
O
4
0,1 M.
Gii:
H
2
C
2
O
4
H
+
+ HC
2
O
4
-
(1) K
a1
= 10
-1,25

HC
2
O
4
H
+
+ C
2
O
4
2-
(2) K
a2
= 10
-4,72

H
2
O H
+
+ OH
-
(3) K
w
= 10
-14

K
a1
> K
a2
>> K
w
Trong dd tn ti ch yu cn bng (1) v (2)
MK: H
2
C
2
O
4
; H
2
O
H
2
C
2
O
4
H
+
+ HC
2
O
4
-
(1) K
a1
= 10
-1,25

H
2
C
2
O
4
2H
+
+ C
2
O
4
2-
(2) K
a2
= K
a1
.K
a2
= 10
-5,52

H
2
O H
+
+ OH
-
(3) K
w
= 10
-14

KP:
|H
+
| = |OH
-
| + |HC
2
O
4
-
| + 2 |C
2
O
4
2-
|
Nu K
a1
>> K
a2
> K
a3
.> K
an
Tnh theo cn bng (1) coi nh l n axit
kin trn khng tho mn Tnh theo k proton
147
| | | |
| | | |
4 2 2 2 1 4 2 2 1
4 2 2 2 1 4 2 2 1
2
2
O C H K K O C H K K h
h
O C H K K
h
O C H K
h
K
h
a a a w
a a a w
+ + =
+ + =

Gn ng: |H
2
C
2
O
4
|
o
= 075 , 0 .
4 2 2
1
=
O C H a
C K
h
1
= 0,065
Ktra k gn ng:
|H
2
C
2
O
4
|
1
= 0,0535 (M)
Gn ng bc 2:
h
2
= 0,055 |H
2
C
2
O
4
|
2
= 0,049 (M)
Gn ng bc 3:
h
3
= 0,0526 |H
2
C
2
O
4
|
3
= 0,0464 |H
2
C
2
O
4
|
2

Kt qu lp pH = - lg 0,0526 = 1,28
4. Dung dch m:
+ HA v A
-
: Thng gp m amoni ( NH
4
+
v NH
3
); m axetat ( HAc, Ac
-
)
+ Mui axti ca mt a axit: VD: NaHCO
3
; H
2
PO
4
-

Bi 10: (THPT Chu Vn An - Ninh Thun)
Tnh pH ca
a/ Dung dch Na
2
HPO
4
0,1M
b/ Dung dch NaH
2
PO
4
0,1M
Bit hng s axit cu H
3
PO
4
in li 3 nc: K
1
= 7,61. 10
-2
; K
2
= 6,23.10
-8
;
K
3
= 2,2. 10
-13

Gii:
a/ Na
2
HPO
4
2Na
+
+ HPO
4
2-
(1)
148
0,1 0,1 (M)
HPO
4
2-
H
+
+ PO
4
3-
K
3
= 2,2. 10
-13
(2)
HPO
4
2-
+ H
2
O H
2
PO
4
-
+ OH
-
K
b2
= K
a2
-1
. K
w
=1,61.10
-7
(3)
H
2
PO
4
-
+ H
2
O H
3
PO
4
+ OH
-
K
b1
= K
a1
-1
. K
w
= 1,31.10
-13
(4)
Ta c Kb
2
>> K
3
> K
b1
Trong dd cn bng (3) l ch yu
Tnh gn ng |OH
-
| =
4 2
2
10 . 27 , 1 1 , 0 . 10 . 61 , 1 .

= = C K
b

pOH = 3,9 pH = 14 pOH = 14 3,9 = 10,1
b/ Tng t
pH = 4,1
5. Cn bng to phc hiroxo ca ion kim loi:
Bi 11: Tnh pH trong h NiCl
2
0,1M, bit
*
= 10
-8,94

Gii:
NiCl
2
Ni
2+
+ 2Cl
-

Ni
2+
+ H
2
O Ni(OH)
+
+ H
+
(1)
*
= 10
-8,94

H
2
O H
+
+ OH
-
(2) K
w
= 10
-14

So snh:

*
.C >> K
w
Tnh theo cn bng (1)

Ni
2+
+ H
2
O Ni(OH)
+
+ H
+
(1)
*
= 10
-8,94

C 0,1
| | 0,1 h h h
149
1 , 0 10 10
1 , 0
87 , 4 94 , 8
2
<< = =


h
h
h
pH = 4,97
C. MT S BI TP:
Bi 1: Tnh pH ca dung dch thu c khi trn 30ml dung dch HCOONa 0,04187
(M) vi 20ml dung dch HCl 0,0625 M.
HD:
Tnh thnh phn gii hn: HCOOH 0,025 M; NaCl : 0,025M
So snh cn bng phn li ca HCOOH v H
2
O KQ: pH = 2,182
Bi 2: Tnh th tch dung dch CH
3
COONa 5,00.10
-3
(M) phi ly khi ho tan
trong 1lit nc c dung dch c pH= 7,8
HD:
Vit biu thc KP
| | | | | | | |h COOH CH K
h
K
h COOH CH OH H
a
w
. .
3
1
3
+
= =
Thay gi tr h = 10
-7,8
C = 6,74.10
-4
(M) >> 10
-7,8
C
b/
= || = 6,74.10
-4
(M)
C =
4
3
10 . 74 , 6
1
. 10 . 5

=
+V
V
V = 0,156 l = 156 ml
Bi 3: Tnh cn bng trong dung dch HBr 10
-1,3
(M) v HCOOH 5.10
-2
(M).
S: h = 0,05
Bi 4: Thm 0,2 ml NaOH 2,5.10
-3
(M) vo 1 ml NH
3
5,0.10
-4
(M) ri pha long
thnh 2 lit. Tnh pH ca dung dch thu c?
S:
So snh cc cn bng
K
b
C
2
K
w
Tnh theo k proton:
150
| | | | ( ) | |
| |
3
1
1
4 1
1 NH K
h C K
h NH C OH H
a
w

+ +
+

= =
Gii gn ng lin tc: h = 1,87.10
-8
(M) pH = 7,73
Bi 5: Tnh pH ca dung dch CH
3
COOH 0,1 M v NH
4
Cl 0,02M.
HD: Ka
1
C
1
>> Ka
2
C
2
> K
w
Trong dd cn bng ca CH
3
COOH l ch yu
Tnh theo lut tc dng khi lng
88 , 2 10 . 3 , 1 10
1 , 0
3 76 , 4
2
1
= = =

=

pH x
x
x
K
a

Bi 6: Tnh cn bng v pH trong dung dhc thu c khi trn 3 ml HCOOH
0,03M vi 6 ml CH
3
COOH 0,15M
HD: C
HCOOH
= 0,01 M
C
CH3COOH
= 0,1 M
K
a1
C
1
K
a2
C
2
>> K
w

Cn bng ca 2 axit l ch yu
Tnh theo KP
MK: HCOOH; CH
3
COOH; H
2
O
| | | | | | | | | | | |
+
+ + + = HCOO COO CH HCOO COO CH OH H
3 3

| | | | COOH CH K HCOOH K h
a a 3 2 1
. . + = (1)
Gn ng: p dng l tc dng khi lng cho cn bng HCOOH
| | ) ( 09587 , 0 ) ( 10 . 13 , 4
3
M HCOOH M x = =


dlt/d khi lng cho cn bng ca CH
3
COOH vi nng H
+
= x = 4,13.10
-3
(M)
| | ) ( 00996 , 0 10 . 15 , 4 01 , 0
5
3
M COOH CH = =


Thay vo (1) h
1
= 4,152.10
-3
(M)
151
Kim tra k gn ng: ....
H = 4,152.10
-3
(M) pH = 2,38
Bi 7: Tnh cn bng v pH trong dung dch H
2
S : 0,1 M
HD: K
a1
>> K
a2
Cn bng nc (1) l ch yu pH = 4,01
Bi 8: Tnh pH trong dd Na
2
S.
HD: Tng t pH = 11,95
Bi 9: Thm 20 ml dung dhc NaOH 0,26M vo 40 ml H
3
PO
4
0,06M. Tnh pH ca
dung dch thu c?
HD:
C
NaOH
= 0,087M ; C
H3PO4
= 0,04M
TPGH: HPO
4
-
= 0,033 (M) ; PO
4
3-
: 0,007 (M)
Tnh gn ng: h K
a
.
b
a
C
C
= 4,7.10
-12,32
<< 10
-7
mi trng baz
Tnh theo cc cn bng baz So snh cc cn bng: CB PO
4
3-
l ch yu
pH = 11,4
Bi 10: Cho kh H
2
S i qua dung dch hn hp FeCl
2
0,01M v HCl 0,2M n bo
ho. C kt ta FeS hay khng?
Bit FeS c tch s tan K
S
= 3,7.10
-19

H
2
S c hng s axit K
a1
= 1,0.10
-7
v K
a2
= 1,0.10
-14

Trong dung dch bo ho nng ca H
2
S l 0,1M
HD:
FeCl
2
Fe
2+
+ 2Cl
-

HCl H
+
+ Cl
-

152
Vy trong dung dch hn hp c:
C (H
+
) = 0,2M; C (Fe
2+
) = 0,01M
Trong dung dch c cc cn bng :
H
2
S H
+
+ HS
-
K
a1
= 10
-7

HS
-
H
+
+ S
2-
K
a2
= 10
-14

| | ) ( 10 . 5 , 2
21 2
M S


T
i
= 0,01.2,5.10-21 = 2,5.10
-23
< T
t
= 3,7.10
-19
khng c kt ta FeS xut
hin
Bi 11: Tnh pH, nng CrO
4
2-
; Cr
2
O
7
2-
trong dung dch:
a/ K
2
Cr
2
O
7
0,01M
b/ K
2
Cr
2
O
7
0,01M + CH
3
COOH 0,1M
Cho K
CH3COOH
= 1,8 .10
-5

Cho cc cn bng trong dung dch nc ca Cr ( IV)
HCrO
4
-
+ H
2
O CrO
4
2-
+ H
3
O
+
(1) pK
1
= 6,5
Cr
2
O
7
2-
+ H
2
O 2HCrO
4
-
(2) pK
2
= 1,36
HD:
a/ pK
1
>> pK
2
K
2
>> K
1
Trong dd cn bng (2) l ch yu.
(2) | | ) ( 10 . 26 , 1
2
4
M HCrO

=
Tnh cn bng (1) vi nng | | ) ( 10 . 26 , 1
2
4
M HCrO

= | | ) ( 10 . 31 , 6
5
M H
+
=
pH = 4,2
b/ CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+
(1) 1,8.10
-5

Cr
2
O
7
2-
+ H
2
O 2HCrO
4
-
(2) 10
-1,36

HCrO
4
-
+ H
2
O CrO
4
2-
+ H
3
O
+
(3) 10
-6,5

153
So snh 3 cn bng (2) l ch yu
nng cc ion Cr
2
O
7
2-
v HCrO
4
-
c tnh nh cu a/
So snh 2 cn bng to H
3
O
+
:
K. C
CH3COOH
>> K
1
.C
HCrO4
Cn bng (1) chim u th:
Tnh | |
+
O H
3
theo cn bng (1) | |
+
O H
3
= 1,34.10
-3
(M) pH = 2,87
Tnh | |
2
4
CrO theo cn bng (3) vi nng ca HCrO
4
-
= 1,27.10
-2
(M);
H
3
O
+
=1,34.10
-3
(M)
| |
2
4
CrO = ) ( 10 . 0 , 3
10 . 34 , 1
10 . 27 , 1
. 10
6
3
2
5 , 6
M

=
Bi 12: CO
2
tan trong nc ma to thnh axit cacbonic
a/ Tm pH ca nc ma nm cn bng vi kh quyn.
b/ Tnh nng ion CO
3
2-
trong nc ma nm cn bng vi kh quyn
Cho bit:
CO
2
(k) + H
2
O H
2
CO
3
K
H
= 10
-1,5
mol/l.atm
K
a1
= 4,45.10
-7
; K
a2
= 4,69.10
-11

p sut ca CO
2
trong kh quyn l 10
-3,5
atm
HD:
CO
2
(k) + H
2
O H
2
CO
3
K
H
= 10
-1,5
mol/l.atm
| |
2
3 2
.
CO H
P K CO H = = 10
-1,5
.10
-3,5
= 10
-5
(M)
a/ Ta c K
a1
| |
3 2
CO H >> K
w
; K
a1
> > K
a2
pH ca dd do cn bng
H
2
CO
3
H
+
+ HCO
3
-

| | 10
-5
x x
154
68 , 5 ) ( 10 . 11 , 2 10 . 45 , 4
10
6 7
5
2
1
= = = =

pH M x
x
K
a

b/ Gi y l nng cn bng ca CO
3
2-

HCO
3

-
H
+
+ CO
3
2-
K
a2

| | x x y
y = K
a2
= 4,69.10
-11
M
Bi 13:
Tnh nng ca axit propionic C
2
H
5
COOH (HPr) phi c trong dung dch axit
axetic CH
3
COOH (HAc) 2.10
-3
(M) sao cho
1/ in ly ca axit axetic bng 0,08
2/ pH ca dung dch bng 3,28
Cho K
Hac
= 1,8. 10
-5
; K
HPr
= 1,3.10
-5

HD:
Cn bng:
HPr H
+
+ Pr
-
(1) K
a1
= 1,3.10
-5

HAc H
+
+ Ac
-
(2) K
a2
= 1,8. 10
-5

H
2
O H
+
+ OH
-
(3) K
w
= 10
-14

Thm HPr in li ca HAc gim.
K
a1
, K
a2
>> K
w
Cn bng (3) nh khng ng k.
1/ | | ) ( 10 . 6 , 1 10 . 2 . 08 , 0
4 3
M C Ac

= = =
| | ) ( 10 . 84 , 1 10 . 6 , 1 10 . 2 10 . 2
3 4 3 3
M C HAc

= = =
| |
| |
| |
) ( 10 . 07 , 2
10 . 6 , 1
10 . 84 , 1
. 10 . 8 , 1 .
4
4
3
5
2
M
Ac
HAc
K H
a

+
= = =
155
nh lut bo ton proton:
| | | | | | | | | | | |
+
+ + + = Ac Ac OH H Pr Pr
| |

Pr = 2,07.10
-4
1,6.10
-4
= 4,7.10
-5
(M)
l t/d kl cho cn bng (1)
| |
| || |
) ( 10 . 48 , 7
Pr .
Pr
4
1
M
K
H
H
a

+
= =
nh lut bo ton nng u:
C
HPr
= | | | | ) ( 10 . 95 , 7 Pr Pr
4
M H

= +
b/ pH = 3,28 h = 10
-3,28
(M)
| |
| |
| |
) ( 10 . 93 , 1 .
3
2
M
H K
H
C HAc
a
HAc

+
+
=
+
= | |
3 3 3
10 . 07 , 0 10 . 93 , 1 10 . 2

= = Ac
| |

Pr = 4,55.10
-4
(M)
| |
| || |
) ( 10 . 84 , 1
Pr .
Pr
2
1
M
K
H
H
a

+
= =
C
HPr
= | |
| |
| |
) ( 10 . 885 , 1 . Pr
2 1
M
H
H K
H
a
+
+
=
+

Bi 14:
1. Dung dch A gm c H
2
SO
4
0,05M; HCl 0,18M v CH
3
COOH 0,02M. Thm
NaOH vo dung dch A n nng cu NaOH bng 0,23M th dng ta thu c
dd A
1

a/ Tnh nng cc cht trong dung dch A
1

b/ Tnh pH ca dung dch A
1

c/ Tnh in li ca CH
3
COOH trong dung dch A
1
.
Cho K
a
(HSO
4
-
) = 10
-2
; K
a
(CH
3
COOH) = 10
-4,75

156
2. Trn dung dch X cha BaCl
2
0,01M v SrCl
2
0,1M vi dung dch K
2
Cr
2
O
7
1M
c cc qu trnh sau y xy ra:
Cr
2
O
7

2-
+ H
2
O 2CrO
4
2-
+ 2H
+
K
a
= 2,3.10
-15

Ba
2+
+ CrO
4
2-
BaCrO
4
T
1
-1
= 10
9,93

Sr
2+
+ CrO
4
2-
SrCrO
4
T
2
-1
= 10
4,65

Tnh khong pH c th kt ta hon ton Ba
2+
di dng BaCrO
4
m khng kt
ta SrCrO
4
?
HD:
1. a/ H
2
SO
4
H
+
+ HSO
4
-

0,05 0,05 0,05
HCl H
+
+ Cl
-

0,18 0,18
NaOH Na
+
+ OH
-

0,23 0,23
H
+
+ OH
-
H
2
O
0,23 0,23
Dung dch A
1
: HSO
4
-
: 0,05M; CH
3
COOH: 0,02M; Na
+
: 0,23 M; Cl
-
: 0,18M
b/ HSO
4
-
H
+
+ SO
4
2-
K
a1
= 10
-2

CH
3
COOH CH
3
COO
-
+ H
+
K
a2
= 10
-4,75

H
2
O H
+
+ OH
-
K
w
= 10
-14

K
a1
C
1
>>

K
a2
C
2
> K
w
Trong dd cn bng (1) l ch yu:
Dlt/dkl cho cn bng (1) | | ) ( 018 , 0 M H =
+
pH = 1,74
CH
3
COOH CH
3
COO
-
+ H
+
K
a2
= 10
-4,75

157
0,02 0,018
0,02-y y 0,018+y
y << 0,018 y = 1,93.10
-5
(M) (tho mn) = 9,65.10
-2
%
2. Trong dung dch c cc cn bng:
Cr
2
O
7

2-
+ H
2
O 2CrO
4
2-
+ 2H
+
K
a
= 2,3.10
-15

Ba
2+
+ CrO
4
2-
BaCrO
4
T
1
-1
= 10
9,93

Sr
2+
+ CrO
4
2-
SrCrO
4
T
2
-1
= 10
4,65

k c kt ta hon ton BaCrO
4
v khng c kt ta SrCrO
4
l
| |
+
+

2
2
4
2
1
Sr
CrO
C
T
C
Ba
T

65 , 3
4
93 , 3
10 10


CrO
C
dlt/d khi lng cho cn bng (1) 3,4 pH 3,7
* Bi 15[19, nm 1999]
Dung dch A gm cc cht tan FeCl
3
, AlCl
3
, NH
4
Cl v CuCl
2
(nng mi
cht xp x 0,1M).
1. Dung dch A c phn ng axt, baz, trung tnh ? ti sao ?
2. Cho H
2
S li chm qua dung dch A cho n khi bo ho th c kt ta v
dung dch B. Hy cho bit thnh phn cc cht trong kt ta v trong dung dch B.
3. Thm dn NH
3
vo dung dch B cho n d. C hin tng g xy ra ? vit
cc phng trnh phn ng ion gii thch.
* Mc ch ca : Nhm kim tra, nh gi k nng phn tch, vn dng
thuyt axt, baz gii thch v d on phn ng trong dung dch, nh gi c
cn bng ch yu, t kt lun dung dch c phn ng g ?
158
* Hng dn gii :
1. Dung dch A c phn ng axt v c d H
3
O
+

2. Cho H
2
S li qua dung dch n bo ho c phn ng.
Cu
2+
+ H
2
S = CuS + 2H
+
v 2Fe
3+
+ H
2
S = 2Fe
2+
+ S+ 2H
+

V vy, trong kt ta c : CuS v S v B : Fe
2+
, Al
3+
, NH
4
+
, H
+
, Cl
-
v H
2
S
3. Thm NH
3
cho n d vo B th c cc cn bng sau :
NH
3
+ H
+
NH
4
+
v

Fe
2+
+ S
2-
= FeS
2NH
3
+ H
2
S = 2NH
4
+
+ S
2-
v Al
3+
+ 3NH
3
+3H
2
O= Al(OH)
3
+ 3NH
4
+
Nh vy s c kt ta FeS (en) v Al (OH)
3
(keo trng).
Bi 16: Lp 12 [19, nm 1997]
* bi : Dng 94,96 ml H
2
SO
4
5% (D = 1,035 g/ml) va tc dng vi
2,80 gam cht X, thu c mui Y v cht Z.
1. X, Y, Z c th l nhng cht no ? Hy gii thch c th v vit phng
trnh phn ng ho hc minh ho.
2. Nu sau qu trnh trn thu c 7,60 gam mui Y th s c bao nhiu
lng cht Z ? Bit X l mt trong cc cht: CaO, MgO, NaOH, KOH, Zn, Fe.
* Mc ch ca : Nhm kim tra kin thc v d on sn phm phn ng
da vo mt s phn ng quen thuc, k nng tnh ton trn phng trnh.
* Hng dn gii : 1. Ta c : ) ( 05 , 0
98 100
5 035 , 1 96 , 94
4 2
mol n
SO H


=
Theo gi thit : X + H
2
SO
4
= Y + Z (1)
159
+ Xt : TH1 ; n
X
:
4 2
SO H
n
4 2
1 : 1
SO H X
n n = = = 0,05
M M
X
= 56
05 , 0
80 , 2
= =
n
m
(g/mol) X tho mn l: Fe, CaO, KOH
Khi : Y tng ng l : FeSO
4
, CaSO
4
, KHSO
4
.
Z tng ng l : H
2
, H
2
O, H
2
O.
+ Xt TH2 : n
X
:
4 2
SO H
n = 2 : 1 n
X
= 2
4 2
SO H
n = 2 x 0,05 = 0,1.
M
X
= 28
1 , 0
80 , 2
= (g/mol) d thy khng c X no tho mn.
2. Theo (1) n
Y
= n
X
=
4 2
SO H
n = 0,05 M
Y
= ) ( 152
05 , 0
6 , 7
g =
M Y c dng ASO
4
A = 56 (vc) Vy X : Fe l tho mn
m
Z
= ) ( 1 , 0 2 05 , 0
2
g m
H
= = hay 0,05 x 22,4 = 1,12 lt
Bi 17: [19, nm 2000]
* bi : 1. Tnh in li ca dung dch CH
3
NH
2
0,010 M
2. in li thay i ra sao khi :
a) Pha long dung dch ra 50 ln.
b) Khi c mt dung dch NaOH 0,001M
c) Khi c mt dung dch CH
3
COOH 0,001M
d) Khi c mt dung dch HCOONa 1,00M.
Bit : CH
3
NH
2
+ H
+
CH
3
NH
3
+
K = 10
10,64
160
CH
3
COOH CH
3
COO
-
+ H
+
K = 10
-4,76

* Mc ch yu cu : Kim tra kin thc ca hc sinh v k nng tng hp
phng trnh phn ng tnh in li v cc yu t nh hng ti in li .
* Hng dn gii :
1. Xt cn bng : CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
(1) K
b
= 10
-3,36
C
0
C
[] C - x x x
K
b
= M x
x
x
x C
x
3 36 , 3
2 2
10 . 89 , 1 10
01 , 0

= =

Vy = % 9 , 18 100 =
C
x

2. in li thay i :
a. Pha long dung dch : C'
M

=
4
10 . 2
50
01 , 0
50

= =
M
C
Tng t = 75,5%.
Nhn xt: tng khi pha long dung dch.
b. Khi c mt NaOH 0,001M
+ CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
(1) K
b
= 10
-3,36
C
0
0,01 10
-3
(Do NaOH phn ly)
[] 0,01 - x x 10
-3
+ x
K
b
= M x
x
x x
3
3
10 . 49 , 1
01 , 0
) 10 (

+
= % 9 , 14 100 .
10
10 . 49 , 1
100 .
2
3
= =

C
x

Nhn xt: gim v [OH
-
] tng lm chuyn dch cn bng (1) sang tri.
c. Khi c mt CH
3
COOH 0,0010 M
161
+ Xt cn bng :
CH
3
COOH CH
3
COO
-
+ H
+
K'
a
= 10
-4,76
CH
3
NH
2
+ H
+
CH
3
NH
3
+
K
a
-1
= 10
10,64

Phn ng : CH
3
COOH + CH
3
NH
2
CH
3
NH
3
+
+ CH
3
COO
-
K = 10
5,88
V K kh ln phn ng trn xy ra hon ton.
Do vy, sau phn ng:
3 3
10 . 9 ; 10
2 3 3
3 3

= = =
+
NH CH COOH CH
NH CH
C C C
+ Cn bng ch yu trong dung dch :
CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
(1) K
b
= 10
-3,36
C
0
9.10
-3
10
-3

[] 9.10
-3
- x 10
-3
+ x x
K
b
= M x
x
x x
3 36 , 3
3
3
10 . 39 , 1 10
10 . 9
) 10 (

= =

+

[CH
3
NH
3
+
] = 10
-3
+ x = 2,39.10
-3
M. Vy = % 9 , 23 100 .
10
10 . 39 , 2
2
3
=


Nhn xt : tng v CH
3
NH
2
tng tc vi CH
3
COOH.
d) Khi c mt HCOONa 1,00 M
HCOO
-
+ H
2
O HCOOH + OH
-
(2) K'
b
=
25 , 10
75 , 3
14
10
10
10

=
So snh K
b
= 10
-3,36
>> K'
b
= 10
-10,25
Cn bng (2) khng nh hng
nhiu n (1). Do vy, hu nh khng thay i hay 18,9%.
162
Bi 18: Lp 12 [19, nm 2005]
* bi : Bng dung dch NH
3
, ngi ta c th lm kt ta hon ton ion Al
3+

trong dung dch nc dng hiroxit, nhng ch lm kt ta c mt phn ion
Mg
2+
trong dung dch dng hiroxit.
Hy lm sng t iu ni trn bng cc php tnh c th. Cho bit: Tch s
tan ca Al(OH)
3
l 5.10
-33
; tch s tan ca Mg(OH)
2
l 4.10
-12
; hng s phn ly
baz ca NH
3
l 1,8.10
-5
.
* Mc ch ca : Nhm kim tra v nh gi kin thc ca hc sinh v kt
ta phn on, k nng so snh, tng hp cc cn bng trong dung dch.
* Hng dn gii : + Xt cc cn bng :
Al
3+
+ 3NH
3
+ 3H
2
O Al(OH)
3
+ 3NH
4
+
(1) K
Mg
2+
+ 2 NH
3
+ 2H
2
O Mg(OH)
2
+ 2NH
4
+
(2) K'
+ lm sng t Al
3+
kt ta hon ton bi di dng Al(OH)
3
bng dung
dch NH
3
th ch cn chng minh K rt ln. Tng t th K' nh.
Thc vy : (1) l t hp ca 2 cn bng sau :
3x NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
3

Al
3+
+ 3OH
-
Al(OH)
3

1
) (
3

OH Al
T

K = K
b
3
.
1
) (
3

OH Al
T = 1,2 . 10
18
rt ln chng t (1) xy ra hon ton.
Cn cn bng (2) l t hp ca 2 cn bng sau :
2x NH
3
+ H
2
O NH
4
+
+ OH
-
K
b
2

Mg
2+
+ 2OH Mg(OH)
2

1
) (
2

OH Mg
T
163
K = K
b
2
.
1
) (
2

OH Mg
T = 81

K' khng nh nhng cng khng ln (2)
xy ra hon ton. Vy iu khng nh u bi l ng.

















164
Chuyn 6
C ch phn ng A
E
v S
E

T Ha hc, trng THPT chuyn H long, Qung Ninh
A . Cc khi nim c bn - Phn loi c ch phn ng
1. Cc kiu phn ct lin kt cng ho tr - tiu phn trung gian.
Do lin kt trong phn t hp cht hu c l lin kt CHT ( C - X ). Cp e
lin kt c th b chia ct theo cc cch sau:
a. Phn ct ng li: mi nguyn t lin kt sau khi b t ra vn cn gi 1e :
S phn ct ng li.
-> S phn ct ng li to ra cc gc t do.
VD: Cl - Cl Cl 2
as

.

b. Phn ct d li: cp e lin kt thuc hn v 1 trong 2 nguyn t lin kt
S phn ct di li.
* Nu cp e lin kt thuc v nguyn t X in tch (+) tp trung nguyn
t C Cacbcation.

CH
3
-C-CH
3
Cl
CH
3
CH
3
-C-CH
3
CH
3
Cl
+
+

* Nu cp e lin kt thuc v nguyn t C in tch (-) tp trung nguyn
t C Cacbanion.
165
Gc t do, Cacbocaton, Cacbanion l nhng tiu phn trung gian trong phn ng.
2. Cht electrophin v cht Nucleophin.
- Trong phn ng c s phn ct d li cc tiu phn phi tng tc vi nhau theo
lc tch in.
* Loi tiu phn c i lc vi electron gi l cht electrophin => d nhin cc
cht ny l nhng ion dng nh: cacboncation, NO
) (
2
+
, H
+
hoc cc phn t cha
nguyn t mang in tch dng do s phn cc mnh ca cc lin kt nh SO
3
, I-
Cl
* Loi tiu phn c i lc vi mnh vi cc trung tm tch in dng gi l
cht Nucleophin cc cht ny l nhng ion m nh cacbanion, HO
-
, Br
--
, CH
3
O
-
...hoc cc phn t cha cp e cha lin kt :
H
2
O, NH
3
, CH
3
OH
..
.. ..

3. C ch phn ng
- L ton b cc bc xy ra ni tip nhau dn ti sn phm.
- Tu theo kiu phn ct lin kt C-X v theo tc nhn phn ng ngi ta chia
c ch phn ng thnh 3 loi.
+ Nu phn ct ng li, tc nhn phn ng l gc t do : C ch gc t do
+ Nu phn ct d li , tc nhn phn ng l cht electrophin : C ch
electronphin
+ Nu phn ct d li, tc phn phn ng l cht Nucleophin : C ch
Nucleophin.
Ngi ta thng thm tn phn ng: Phn ng th (S), phn ng cng (A),
phn ng tch (E) trc tn ca c ch :
166
V d nh: S
R
, S
E
, A
E

B. Gii thiu 2 c ch phn ng thng gp trong chng trnh ho hu c
A
E
: c ch cng electrophin, xy ra anken (C =C) hoc ankin (C C)
S
E
: c ch th electrophin, xy ra nhng hp cht c vng thm
(V d : vng benzen)
Vy ti sao cc lin kt bi (=, ) v vng thm u c phn ng lin quan
n tc nhn ny? n gin v y l cc h giu e

nn tc nhn electrophin ( tc
nhn mang in tch dng) d tn cng vo.
I. c im c ch A
E
v S
E
.
1. C ch A
E

- Gm 2 giai on c ch ny tri qua cc bc to phc pi, ion cabenium,
...; v mt ha lp th c cng trans (ch yu) hoc cng cis).

Giai on 1:



Giai on 2:

EY: Hal
2
, Hal - Hal', HX, HOH, HOX, H
2
SO
4
..
VD: EY l HBr
C = C +
) ( S ) ( S
Y E
+
C -- ' C
) ( +
+ Y
(-)

Chm, quyt
nh tc
phn ng
C - ' C
) ( +
+
) (
Y

C - ' C

167
HBr
> < +
+ Br H
) (

(1) CH
2
= CH
2
+ H
+
CH
3
-
) (
2
CH
+

(2) CH
3
CH
(+)
2
+
> <
Br CH
3
CH
2
Br
Ch : Nu trong mi trng phn ng c mt cc tc nhn Nucleophin nh
.. ..
H
2
O, CH
3
OH
, I
< - >
th ngoi (2) cn c:









2. C ch S
E

Gm 2 giai on
Giai on 1



CH3 -
) (
2
CH
+
+
H2O
CH3OH
I
(-)

CH3CH2 -
2
) (
H O
+
CH3CH2OH
-H
+

CH3CH2 -
3
) (
CH O
+
CH3CH2OCH3
-H
+

H
CH3CH2I
+
) (
E
+

C
+
E
H
Phc
chm, quyt nh tc
phn ng
168

E

Giai on 2


... SO , R , O N : E
3 2
) ( + + +

VD : Phn ng nitro ho benzen, xt H
2
SO
4

H
2
SO
4
H
+
+ HSO
4
-











1.
C
+
E
H
Phc
Y
(-)

+ HY
H - O - NO2 + H
+
H2 -
) (
O
+
- NO2


H2 -
) (
O
+
- NO2 H2O +
) (
2
+
O N
H2SO4
+
2
) (
O N
+

C
+
NO2
H
C
+
NO2
H
NO2
+ H
+

H
+
+ HSO

4
H2SO4
169



Mun gii quyt c cc bi ton lin quan n c ch A
E
, S
E
cn phi c
3 bc phn tch sau y :
+ Tc nhn electrophin (gi tt l E
+
) l g ? (da vo sn phm hoc iu kin
phn ng)
+ Tc nhn electrophin (E
+
) c to ra nh th no?
+ Tc nhn (E
+
) s tn cng vo u ?
II. S to thnh tc nhn electrophin (tc nhn E
(+)
)
Tc nhn E
(+)
l tiu phn c i lc vi electron gi l cht electrophin => d
nhin cc cht ny l nhng ion dng nh: Cacboncation, NO
) (
2
+
, H
+
hoc cc
phn t cha nguyn t mang in tch dng do s phn cc mnh ca cc lin
kt nh SO
3
,
I- Cl
1. Do s phn cc ca phn t nh :






Br(
+)
- Br
(-)
(dung mi phn cc : H2O, CCl4)

) ( S ) ( S
Cl I
+

O


) ( S
S
+
= O
170



2. T qu trnh in ly
HX H
+
+ X
-
(X : Halogen)
3. Do tc dng ca axit
a. T HOX (HOCl)
H-O-Cl
H H-O-Cl
H
H-O-Cl
H
H
2
O + Cl
+
+
+
+
+

b. T HNO
3






c. T anken trong mi trng axit
R - CH = CH
2
+ H
(+)
R-
) (
CH
+
-CH
3

H - O - NO2 + H
+
H -
) (
O
+
- NO2


H -
) (
O
+
- NO2 H2O +
) (
2
+
O N
H2SO4
171
d. T ru trong mi trng axit
R-OH + H
+
R-
) (
2
OH
+

O H
2
R
(+)

e. T anehit, xeton trong mi trng axit








4. Phn ng chuyn dch Hidro R
+
+ R'H R
+

+ RH
iu kin R' l gc bc 3, bn hn R
(+)

VD:


5) S to thnh E
(+)
khi c mt ca AlCl
3
hoc FeBr
3
(hay dng cho phn
ng S
E
)
- Br
2
/FeBr
3
:
) ( S ) ( S
Br Br
+
+ FeBr
3

+
] FeBr [ Br
4
) (_

- I
2
/AgNO
3
: I
2
+ AgNO
3
AgI +
) (
3
) (
NO I

+

- RCl/AlCl
3
: RCl + AlCl
3
R
(+)
[AlCl
4
]
-

R - C = O + H
+
R -
) (
CH
+
- OH

R - C = O + H
+
R -
) (
C
+
-
OH
CH3

CH3 - CH - CH3 + CH3 - C - CH2 -
) (
C
+
- CH3

CH3 -
) (
C
+
- CH3 + (CH3)3 - CH2 - CH - CH3

172






- RCOCl : RCOCl + AlCl
3
RC
+
=O [AlCl
4
]
-


III. S tn cng ca E
(+)
vo lin kt i. Cc vn lin quan n A
E

1. Kh nng phn ng ca lin kt i (Yu t tnh)
Lin kt i cng giu electron th kh nng tip nhn tc nhn E
(+)
cng d ->
tng kh nng phn ng. Vy nhng nhm y e vo lin kt i s lm tng kh
nng cng v ngc li.
VD1:
CH
3
--CH=CH--CH
3
> CH
3
-CH=CH
2
> CH
2
=CH
2
> CH
2
=CH -- Br > CH
2
=CH --COOH
. +I, +H
. +I, +H
- I
- I, -C


VD2:



VD3:

- R(CO)2O/AlCl3: R - C - O - C - R + AlCl3 R -
) (
C
+
[AlCl3 O - C
- R]
(-)

II
CH3O CH = CH2 > CH3 - CH = CH2 > CH2 = CH - COOH


Br
1 : 1
CH3 - C = CH - CH2 - CH2 - CH = CH2 + HBr CH3 - C - CH2 - CH2CH2 - CH = CH2

173




Ch : Kh nng phn ng A
E
ca lin kt ba km lin kt i do nguyn t
Csp c m in ln hn Csp
2
lm cho obitan b gi cht hn v kh phn cc
hn.
2. S tn cng ca E
(+)
vo lin kt i. Quy tc Macopnhicop
VD1:






Nh vy
) (
E
+
s tn cng u tin to ra cation bn hn v to ra sn phm chnh.
VD2:





CH3 - CH = CH2 + H
+

CH3 -
) (
CH
+
- CH3
) (
Br
CH3 - CH - CH3 (sn phm chnh)
(Bn hn)
CH3CH2 -
) (
CH
+
2
) (
Br
CH3CH2CH2 - Br (sn phm ph)
(km bn)
CH2 = CH - COOH + H
+

CH3 -
) (
CH
+
COOH
+
) (
Br
CH3 - CH - COOH (SP ph)

-I, -C Br
) (
CH
+
2 - CH2 COOH
) (
Br
CH2 - CH2 COOH
- I Br
174



Ni dung (Qui tc) Macopnhicop : Phn ng cng Electrophin lun lun xy ra u
tin theo hng hnh thnh Cacbocation trung gian tng i bn hn.
VD3:











Vy sn phm to ra l CH
3
-CHBr-OCO-CH=CH
2


3. So snh kh nng phn ng ca mt s tc nhn phn ng
a. Halogen
F
2
> Cl
2
> Br
2
> I
2
(do kh nng phn ng ca F
) ( +
> Cl
(+)
> Br
(+)
> I
(+)

)
(1) (2) 2' 1'
CH2 = CH - O - CO - CH = CH2 + HBr
1 : 1




Nu H
+
vo (1) c cation l CH
3
-
) (
CH
+
-
. .
O - C - CH = CH
2


O
+ C (bn hn)

Nu +H vo (1') c cation l CH = CH - O - C -
) (
CH
+
- CH
175
F
2
: Gy n, I
2
: Phn ng km
b. ihalogen
VD1: So snh kh nng phn ng ca Br
2
, BrCl, Cl
2

Vi Br
2
: Tc nhn E(+) Br
(+)

BrCl Br
(+)


nhng do Br
S(+)
Cl
S(-)
phn cc hn nn BrCl phn ly ra Br
+
tt hn nn BrCl >
Br
Vi BrCl v Cl-Cl
Mc d Br-Cl phn ly tt hn Cl-Cl, nhng do kh nng phn ng ca Cl
(+)

mnh hn Br
+
nn BrCl < Cl
2

Vy Br
2
< BrCl < Cl
2
c. Cc axit HX
HF << HCl < HBr < HI
do lc axit tng dn -> kh nng in ly ra H
+
tng dn.
IV. Cc vn lin quan n c ch S
E

1. Nhm th hot ho, nhm th phn hot ho (Yu t tnh)
Nu nhn thm cng giu e -> kh nng tip nhn E
(+)
cng ln -> Kh nng phn
ng S
E
ln.

Nh nhau
176




Lm tng kh nng phn ng => hot ho nhn thm






Gim mt e trong vng -> gim kh nng phn ng -> phn hot ho nhn
thm.
2. Nhm nh hng (o, p ), c nhm nh hng m (Yu t ng).
a. nh hng m
u l nhng nhm c hiu ng -I, -C (hoc -F). Hy quan st 3 mc sinh ra
lm tng mt e
trong vng
Nhng nhm
+ I, +H: Ankyl (CH3, CH3CH2
+ C : -CH = CH2, C6H5
+ C > -I :
. .
OH ,
. .
NH2,
. .
OR
Nhng nhm
- I: -N
+
R3, -S
+
R2
- I,-C : - NO2, - C - R , - CH = O, - COOH

O
- I > + C: Halogen
-I, -F: CF3
177

C 3 phc u km bn do hiu ng -C, nhng hiu ng v tr m yu hn do
nhng nguyn t mang in tch (+) xa nhau hn.
=> Sp (m) u tin hn.
b. nh hng o, p
u l nhng nhm c hiu ng +H hoc +C
Xt 3 phc sinh ra







OH
NO2 +1/3
+1/3
+1/3


OH
NO2
+1/3
+1/3
+1/3


OH
NO2



+1/3
+1/3
+1/3


H

H

H

(o) (p) (m)
178
+ C lm cho phc v tr o hoc p tr ln bn vng hn so vi m nh s
gii to din tch (+).
-> D hiu ti sao halogen phn hot ho nhng vn nh hng o, p do:
- Trng thi tnh: Halogen c I > + C: Mt e trong vng gim -> Kh
nng phn ng gim.
- trng thi ng: Halogen th hin hiu ng +C nn lm cho phc v
tr o, p bn vng hn m .










3. Quy lut th hp cht thm khc
3.1 Dn xut 2 ln th ca benzen C
6
H
4
XY
nh
hng
O
Mnh
Trung bnh
Yu
NH2, NHR, NR2, OH
OR, NH-COR
R, C6H5
Mnh
Trung bnh
Yu
Hot
ho
Yu
nh
hng
m
Yu
Trung bnh
Mnh
CH = O, COR, COOH
SO3H, CN
NO2, NR3, SR2
TB
Mnh
Phn
hot
ho
Br, Cl, F
179
- Nu X, Y c tnh nh hng ging nhau ( cng (o, p) hoc cng m ) ->
nhm no c tnh nh hng mnh hn s quyt nh.






- Nu X nh hng (o, p) (X c +C) , Y nh hng (m) (X c -C) nhm X
s quyt nh.




3.2 Naphtalen:
C kh nng phn ng S
E
cao hn benzen (do vng benzen bn cnh c hiu
ng +C -> in tch (+) c gii to, mt khc mt e trong naptalen cng
nhiu hn benzen (10e

trn 8C trong khi benzene ch c 6e trn 6C).
V tr d th hn do phc ng vi v tr n nh hn .

OH
Cl
OH
Cl
OH
Cl
NO2
CHO
NO2
CHO
NO2
CHO
Rt kh khn
OH
CHO
OH
CHO
OH
CHO
180








3. Piriin:
C kh nng phn ng S
E
km benzen (10
7
ln) (do c N c m in ln c
hiu ng I lm gim mt e trong vng ), nguyn t N nh hng v tr 3 (m).






C. Mt s v d v c ch A
E
v S
E
.
I. C ch A
E

1.
+C -C
-
C
C(+)
1
2
3
4 5
6
7
8
N
N
OH
N
OH
N
OH
N
181
Cho phn ng CH
2
= CH
2
+ Br
2
(dung mi CH
3
OH). Nu thm dung dch
NaCl vo hn hp phn ng th thu c sn phm no ? Nu thm HCl vo hn
hp phn ng th thu c sn phm no ? Vn tc phn ng trong mi trng hp
trn c thay i khng ? Gii thch.
Hng dn gii:
* Giai on 1: (l giai on quyt nh tc phn ng ) tiu phn tch in
dng tn cng vo nguyn t C mang lin kt
* Giai on 2 : Anion tn cng vo phn dng ni trn to ra sn phm cng.

* i vi thm NaCl : Br
2
Br
+
+ Br

.
Br - CH
2
- CH
2
-Br

CH
2
= CH
2
+ Br
+
Br - CH
2
- CH
( )
2
+
Br - CH
2
- CH
2
- Cl

Br - CH
2
- CH
2
-
OCH
3

* i vi thm HCl : HCl H
+
+ Cl

.
Khi Ion H
+
s tn cng trc
CH
3
- CH
2
- Cl

CH
2
= CH
2
+ H
+
CH
3
- CH
( )
2
+
CH
3
- CH
2
- Br
CH
3
- CH
2
- O - CH
3

CH
3
O


Br


Cl


Cl


CH3O



Br


182
V giai on 1 quyt nh tc phn ng nn thm NaCl khng lm thay i
tc phn ng, cn thm HCl (H
+
) s lm thay i ng k tc phn ng.
2 .
a. 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm, trong
c A l 2-clo-3-metylbutan v B l 2-clo-2-metylbutan. Bng c ch phn ng,
hy gii thch s to thnh hai sn phm A v B.
b . 2-metylbuten-2 phn ng vi axit clohidric. Trnh by c ch ca phn
ng, cho bit sn phm chnh v gii thch?
Hng dn gii:
H
+
CH
3
-CH-CH-CH
3
CH
3
CH
3
-CH-CH
2
-CH
2
CH
3
+
+
chuyn v
(I)
(II) (III)
2-Clo-2-metylbutan 2-Clo-3-metylbutan
CH
3
-C-CH
2
-CH
3
CH
3
+
Cl
-
Cl
-
CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH-CH-CH
3
CH
3
Cl
CH
3
-C-CH
2
-CH
3
CH
3
Cl
1.

Do cacbocation bc hai (II) c kh nng chuyn v hirua to thnh cacbocation bc ba (III) nn to thnh
hai sn phm A, B.
H
+
Cl
-
CH
3
-C-CH
2
-CH
3
CH
3
+
(I)
CH
3
-C-CH-CH
3
CH
3
+
(II)
2-Clo-2-metylbutan
CH
3
-C=CH-CH
3
CH
3
Cl
-
CH
3
-C-CH
2
-CH
3
CH
3
Cl
2-Clo-3-metylbutan
CH
3
-CH-CH-CH
3
CH
3
Cl

2-Clo-2-metylbutan l sn phm chnh.
Do cacbocation bc ba (I) bn hn cacbocation bc hai (II), mt khc do cacbocation bc hai (II) c kh
nng chuyn v hirua to thnh cacbocation bc ba (I) nn sn phm 2-clo-2-metylbutan l sn phm
chnh.
3 . Khi c tc dng ca axit , geraniol chuyn ho thnh -Terpineol c cu
trc sau:
CH
3
-C=CH-CH
2
-CH
2
-C=CH-CH
2
OH
CH
3
CH
3
H
+
C H
3
CH
3
CH
3
OH

183
geraniol -Terpineol
ngh c ch cho qu trnh chuyn ho ny.
Hng dn gii:

4.
CH
3
-C=CH-CH
2
-CH
2
-C=CH-CH
2
OH
CH
3
CH
3
H
O H
2
CH
3
-C=CH-CH
2
-CH
2
-C=CH-CH
2
CH
3
CH
3
CH
3
-C=CH-CH
2
-CH
2
-C=CH-CH
2
CH
3
CH
3
C H
3
C H
3
CH
3
O H
2
CH
3
C H
3
C H
3
OH
2
H
CH
3
CH
3
C H
3
OH
+
+
+
+
+
+
+


Khi cho Isobutilen vo dung dch H
2
SO
4
60% un nng ti 80
o
C thu c
hn hp gi tt l i-Isobutilen gm 2 cht l ng phn ca nhau A v B. Hidro
ho hn hp ny c cht C l 2,2,4-trimetylpentan. C cng c th c iu ch
bng phn ng trc tip ca Isobutilen vi Isobutan khi c mt H
2
SO
4
c. Vit c
ch phn ng gii thch s to thnh A, B, C.
Hng dn gii:
A v B l i-isobutilen (C
4
H
8
) nn c CTPT l C
8
H
16
. (a=1) . A v B khi cng H
2

ra C A v B c b khung Cacbon ging C .
184
CTCT ca C:
CH
3
-C-CH
2
-CH-CH
3
CH
3
CH
3
CH
3

C ch to A v B: H
2
SO
4
H
+
+ HSO
4
-

CH
3
-C-CH = C-CH
3
CH
3
CH
3
CH
3
CH
2
=C-CH
3
CH
3
H
CH
3
-C-CH
3
CH
3
CH
2
=C-CH
3
CH
3
CH
3
-C-CH
3
CH
3
CH
3
-C-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
2
- C = CH
2
CH
3
CH
3
CH
3
H
+
+
+
+
+
+
+
+
+
+

(A) (B)
C ch to C khi Isobutilen p vi Isobutan khi c mt H
2
SO
4
c: (thm H vo
cng thc ca isobutan)
H
2
SO
4
H
+
+ HSO
4
-

185
CH
2
=C-CH
3
CH
3
H
CH
3
-C-CH
3
CH
3
CH
2
=C-CH
3
CH
3
CH
3
-C-CH
3
CH
3
CH
3
-C-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
3
CH
3
CH
3
-C-CH
2
-CH-CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
3
CH
3
+
+
+
+
+
+
+
+
+
+

2 . Bi tp v c ch S
E

1.
a. Cht no c kh nng phn ng th S
E
cao nht trong s cc hp cht sau:
p-C
6
H
4
(CH
3
)
2
, C
6
H
5
CH
3
, p-C
6
H
4
(COOH)
2
, p-CH
3
C
6
H
4
COOH, m-C
6
H
4
(CH
3
)
2
.
b. Cht no cho sn phm m-Nitro vi t l % cao nht :
(+) (+) (+)
C
6
H
5
-CH
2
N(CH
3
)
2
, C
6
H
5
-N(CH
3
)
3
, C
6
H
5
-CH
2
-CH
2
-N(CH
3
)
3

c. Cht no b Nitro ho cho sn phm o-Nitro vi % thp nht
C
6
H
5
Hal, vi Hal l : Cl, Br, F,I
Hng dn gii:

a.
CH
3
CH
3
>
CH
3
CH
3
>
CH
3
>
CH
3
COOH
>
COOH
COOH
.
186
b. Sp m- nitro vi t l % cao nht khi c nhm th ht e (-I, hoc -C) mnh
nht.
(+) (+) (+)
3 nhm th - CH
2
- N(CH
3
)
2
, -N(CH
3
)
3
,-CH
2
-CH
2
-N(CH
3
)
3
u khng c C ,
ch c I m hiu ng I gim theo mch Cacbon vy cht cho sp m-nitro
nhiu nht l : C
6
H
5
-N
+
(CH
3
)
3

c. Halogen l nhm c I > +C , phn hot ho (-I ) nhng vn nh hng o,p
(do c +C ).
- 2 yu t quyt nh t l sn phm o-p :
+ yu t khng gian (1): T F n I: Th tch tng th sn phm octo gim, para
tng. + Yu t hiu ng (2): T I n F , hiu ng I tng lm gim bn ca
phc xichma nn phc xichma v tr octo ca Flo km bn nht.
Yu t 2 ng vai tr quyt nh nn C
6
H
5
F cho % sn phm cto thp nht.
2 . "C bn hp cht thm : C
6
H
5
-NH
2
, C
6
H
5
-CH
3
, C
6
H
5
-NO
2
, C
6
H
6
vi cc tnh cht
sau:
Cht phn ng A B C D
Nc Br
2
Khng ph. Khng ph.ng C ph. t
o

thng
Khng ph.
Br
2
/Fe C phn ng C phn ng Ph.ng 0
o
C
khng cn Fe
Ch phn ng
khi un
nng
HNO
3
/H
2
SO
4
C phn ng
khng cn
H
2
SO
4

C phn ng Ph.ng chm
(c th to ra
sn phm meta)
Ch phn ng
khi un
nng
a/ Xc nh k hiu A,B,C,D cho mi cht .
b/ Sp xp cc cht theo th t tng dn v kh nng th nguyn t Br vng
Benzen v gii thch ?
187
c/ Sp xp cc cht theo th t tng dn v kh nng th nhm NO
2
vng Benzen
v gii thch v sao th t ny khc vi th t phn (b) ?
*A l C
6
H
5
-CH
3
; B l C
6
H
6
; C l C
6
H
5
-NH
2
; D l C
6
H
5
-NO
2
.
* Th t phn ng th nguyn t Br : D < B < A < C
Gii thch: .
V phn ng th nguyn t Hidro vng benzen thuc loi th Electrophin tc
l tng tc gia h electron ca vng benzen vi tc nhn mang in dng
nn mt electron trong vng benzen cng ln th phn ng cng d dng.Ly
C
6
H
6
lm trung gian ta thy: - Cc nhm -CH
3
; -NH
2
thuc loi nhm th hot
ng ha (nhm y e ; +I,+C) lm tng mt e ca vng benzen,cn nhm-
NO
2
thuc loi nhm th phn hot ha (ht e; -I,-C) lm gim mt e ca
vng benzen nn kh nng phn ng th ca A,C > B > D.
-So snh gia A v C th trong phn t A do nguyn t N cn i e t do nn c s
lin hp p- vi vng benzen in tch dng c th gii to ti nguyn t oxi
mt e trong vng benzen ca C > so vi ca A kh nng phn ng th C >A.
* Th t phn ng th nhm NO
2
: C < D < B < A
Gii thch : Do qu trnh proton ha nhm NH
2
ca C
6
H
5
-NH
2
bi HNO
3
(v c
th c H
2
SO
4
) theo phng trnh: C
6
H
5
-NH
2
+ HNO
3
C
6
H
5
-NH
3
+
NO
3
-

NH
3
+
mang in tch dng c hiu ng I rt mnh Kh nng th cn km
hn so vi C
6
H
5
-NO
2
. Sau , di tc dng ca HNO
3
thng thu c sn
phm th nhm NO
2
v tr meta

NH
3
HNO
3
H
2
SO
4
NH
3
NO
2
+
+

188

3.
a. Cho A l 1-metyl-4-isopropylbenzen c iu ch t toluen v
CH
3
CH
2
CH
2
OH . Vit phng trnh phn ng v c ch phn ng . Gii
thch
b. Cho A tc dng vi (CH
3
)
3
C-OH c mt H
2
SO
4
c thu c cht B . Gii
thch c ch hnh thnh B
c. Nu thay A bng 1,4- imetylbenzen v cng cho tc dng vi ru trn c
mt H
2
SO
4
c th thu c sn phm c CTCT nh th no? Vit c ch
hnh thnh.
B c CTCT:

C H
3
CH
3
CH
3
C H
3
C H
3

189
a.
CH
3
-CH
2
-CH
2
-OH
H
O H
2
CH
3
-CH
2
-CH
2
CH
3
-CH-CH
3
CH
3
CH
3
C(CH
3
)
2
H
H
CH
3
C(CH
3
)
2
+
+
+
+
+
+
+

190
b. H
2
SO
4
H
+
+ HSO
4
-
CH
2
=C-CH
3
CH
3
H
CH
3
-C-CH
3
CH
3
CH
3
-C-CH
3
OH
CH
3
H
O H
2
CH
3
-C-CH
3
CH
3
CH(CH
3
)
2
C H
3
CH
3
-CH-CH
3
CH
3
C-CH
3
C H
3
CH
3
C-CH
3
C H
3
CH
3
C H
3
CH
3
CH
3
C
CH
2
-C-CH
3
CH
3
CH
3
CH
3
C
CH
2
-C-CH
3
CH
3
C H
3
H
C H
3
C H
3
H
C H
3
CH
2
=C-CH
3
CH
3
(*)
CH
3
-C-CH
3
CH
3
H
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+

c. Nu thay A bng 1,4- imetylbenzen v cng cho tc dng vi ru trn c mt
H
2
SO
4
c th thu c sn phm c CTCT:
CH
3
CH
3
CH
3
-C-CH
3
CH
3
OH
H
2
SO
4
CH
3
CH
3
C(CH
3
)
3
O H
2
+
+

191


C ch: . H
2
SO
4
H
+
+ HSO
4
-

CH
3
-C-CH
3
OH
CH
3
H
O H
2
CH
3
-C-CH
3
CH
3
CH
3
-C-CH
3
CH
3
C H
3
CH
3
C H
3
CH
3
(CH
3
)
3
C
H
C H
3
CH
3
(CH
3
)
3
C
H
C H
3
CH
3
(CH
3
)
3
C
H
+
+
+
+
+
+
+
+
+

Thu c sn phm bnh thng do khng th c qu trnh (*).
4 . un nng Stiren vi H
2
SO
4
ta thu c hp cht c CT:

CH
3

Hy gii thch c ch hnh thnh sn phm trn.
H
2
SO
4
H
+
+ HSO
4
-

192

CH
3
CH=CH
2
H
CH-CH
3
CH=CH
2
CH-CH
2
-CH-CH
3
CH
3
H
H
+
+
+
+
+
+
+


III.Bi tp ngh
Bi 1 .(HSGQG-1997):Cho phng trnh phn ng sau:
OH
H
2
SO
4
85
%
10
0
C
v
O H
2

(A) (B hiu sut 55%)

1.Vit c ch phn ng .
2.Thay A bng C
6
H
5
-CH(CH
3
)-CH
2
-CH
2
-C(CH
3
)
2
OH (A1),
193
C
6
H
5
-CH
2
-CH
2
-C(CH
3
)
2
OH (A2) v tin hnh phn ng trong iu kin tng t
nh trn thu c sn phm tng ng l B
1
(hiu sut 86%)v B
2
(hiu sut 65%).
a.Vit CTCT ca B
1
v B
2
.
b.Ti sao hiu sut phn ng to B
1
v B
2
cao hn to ra B.
Bi 2 (HSGQG-1998) 1.Vit phng trnh phn ng to thnh sn phm chnh khi
cho 1 mol hidrocacbon A tc dng vi cc cht sau:

(A)

a.1 mol HNO
3
(H
2
SO
4
c)
b.1 mol Br
2
c nh sng.
c.KMnO
4
c d,un nng.
d.Trnh by giai on quyt nh tc chung ca mi phn ng a v b.
2.Itbenzen c iu ch vi hiu sut cao theo s phn ng sau:
t
0
C
C
6
H
6
+I
2
+ HNO
3
C
6
H
5
I + NO + NO
2

Cho bit vai tr ca HNO
3
? Nu tn c ch
Bi 3.
a. Vit phng trnh phn ng cng Brom vo propen v ngh c ch phn
ng .
194
b. Vit phng trnh phn ng cng cc halogen dng Br-Cl, I-Cl, I-Br vo
propen v cho bit th t tng tc phn ng theo dy
I
2
< .? .< Br
2
< ? < Cl
2
.
778c. Vit phng trnh phn ng ca Br-Cl vi : Buten-1, penten-2, axit
propenoic, Brom eten. Xp cc cht trn theo th t tng dn tc phn
ng .

Bi 4. Vit CTCT sn phm chnh v vit c ch gii thch.
a.
C
6
H
5
(CH
2
)
4
OH
H
2
SO
4
,
85
%
C
10
H
12

b.
CH
3
-CH
2
-CH
2
-CH=CH
2
H
2
SO
4
, HCHO
C
6
H
14
O
2

g.
CH
2
=CH-COO-CH=CH
2
ICl
C
5
H
6
ClIO
2

Bi 5. Hy phn tch ch ra hng tn cng ca Brom trong mi trng hp sau y:
a/ C6H5CONHC6H5 + Br2/FeBr3 .....
b/

CH
3
CH
2
S OCH
2
CH
3
+ Br2/xt (1:1) .....
c/ CH2=CHCOOCH=CH2 + Br2/H2O (1:1 ) .....
Bi 6.
Trong cc phn ng cng hp Electronphin vo cc hp cht khng no mang
nhm th c i e khng lin kt, cc nhm th ny i khi c s dng nh l
tc nhn Nucleophin ni phn t tn cng vo Cacbocation trung gian hnh
thnh sn phm ng vng . V d s Brom ho axit Cacboxylic cha no i khi c
th khng dn n cc sn phm iBrm ho thng thng m dn n este vng
(cn gi l Lacton) nh phn ng sau y:
195
C
6
H
5
-CH=CH-CH
2
-C
OH
O
+ Br
2
O
C
6
H
5
O
Br
+ Br H

a. Anh ch c cho rng bt k axit cha no no khi phn ng vi Brom u cho
Lacton?
b. S khc nhau gia khi lng mol ca sn phm chnh v khi lng mol
ca axit ban u trong phn ng ca cc axit cha no sau y vi Brm :
- Axit 3- phenyl Propenoic (Axit Xiamic)
- Axit 2- Vinyl Benzoic
Mt khc , phn ng cng ng vng in X- An c th dn n cc ng phn
hnh hc khc nhau ph thuc vo s nh hng ln nhau ca phn t phn ng .
V d Xiclopentaien phn ng vi Anhirit Maleic chjo sn phm cng Eno
hoc Exo ph thuc vo iu kin phn ng :
(4)
+
O
O
O

O
O
O
H
H
+

sn phm cng En(Trans vi C
4
)
(4)
()
O
O
O
H
H
sn phm cng Ex (cis vi C
4
)
196
Vi phn l thuyt a ra trn hy th gii thch cc khm ph thc nghim sau
y:
Khi nhng ng lng bng nhau ca Xiclopentaien v Anhirit maleic c
un nng n 100
o
C th 1 hp cht A duy nht c thnh phn C
9
H
8
O
3
c hnh
thnh . un hi lu cht A vi Metanol d khi c mt Axit mnh s thu c B
(C
11
H
14
O
4
). Nu qu trnh ny c thc hin vi Furan thay cho Xiclobutaien th
s nhn c cht C c cng thc C
10
H
12
O
5
. C 2 B v C phn ng d dng vi
dung dch nc Brom theo cc phng trnh phn ng di y:
C
11
H
14
O
4
(B) + Br
2
+ H
2
O C
10
H
11
BrO
4
(D) + HBr + CH
3
OH
C
10
H
12
O
5
(C) + Br
2
C
10
H
12
Br
2
O
5
(E)
c. Hy a ra cu trc ca A v B v vit phn ng chuyn ho A B
d. Hy a ra cu trc ca C, D v E
Bi 7 . Vic nghin cu 1 hidrocacbon quang hot A ch ra nh sau:
- 0,345 g A lm mt mu hon ton 5 ml dung dch 0,5M Br
2
/CCl
4
.
- Ozon phn cht A cho 1 sn phm duy nht m khi x l sn phm vi I
2

trong dung dch kim th chuyn thnh axit hu c B v nhng tinh th mu
vng c mi tanh (CHI
3
) v tr ln en nhanh ngoi khng kh c thnh phn
C 3,1% H 0,3 % . Axit B l axit c th iu ch t phenol phn ng vi
propilen khi c mt H
2
SO
4
, tip theo hidro ho xc tc sn phm v oxi ho
tip tc bng KMnO
4
trong mi trng axit nhit cao.
- Cng hp HBr lm mt hon ton tnh quang hot.
- Hidro ho A thu c hidrocacbon no AS , cht ny c th iu ch bng cch
khc khi H
2
ho mt trong cc sn phm ch yu ca phn ng inx- An
ca Isopren (imeIsopren) c tn thng thng l Limonen.
Thc hin phn ng hidro ho xc tc axit (tc l phn ng vi H
+
) vi
Limonen . Tip theo l s tn cng ca Cation trung gian vo lin kt i
Enoxiclic v lm bin mt Cacbocation th 2 vi 1 phn t H
2
O, c th sinh
ra 2 Ancol Lixiclic quan trng vi khung C khc nhau . Mt trong cc ancol
ny l Bocneol c mi mnh v khi oxi ho nh cho xeton tng ng . l
197
Campho . Ancol th nht rt bn vi s oxi ho , c khung C ca pinen v n l
thnh phn ch yu ca du thng.
a. Hy a ra cu trc ca A .
b. Vit cc phn ng dng xc nh cu trc ca A.
c. Vit CTCT ca Limonen, Bocneol, pinen.
d. Vit cng thc cu trc ca (+)- campho thin nhin
Bi 8 : Vit cc phng trnh phn ng theo t l s mol 1:1 ca cc cht sau y
vi dung dch Br
2
trong CCl
4
. Gii thch s nh hng phn ng :
a, CH
2
= CH- CH
2
- C CH b, CH
2
= CH- C CH
c, (CH
3
)
2
C= CH- CH
2
- CH= CH
2
d, CH
3
- CH= CH- CH
2
- CH= CHBr





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