Cơ Sở Lý Thuyết Hóa Học Phần Lý Thuyết Va Bài Tập Lê Mậu Quyền

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Bi ging mn C s l thuyt Ho hc
PHN I: CU TO CHT
CHNG I - CU TO NGUYN T
I. M u
1. Cc ht c bn to thnh nguyn t:
* Nguyn t c:
0
- Kch thc khong 1 A ( 10-10 m).

- Khi lng: 10-23 kg.
* Nguyn t gm:
- Ht nhn ( in tch +Z) gm:
+ Proton (p), mp =1,672. 10-27kg, tch in dng + 1,602. 10-19C.
+ Notron(n), mn = 1,675. 10-27 kg, khng mang in .
Ht nhn ca cc nguyn t u bn (tr cc nguyn t phng x).
- Electron(e) ,me = 9,1. 10-31 kg , tch in m - 1,602. 10-19C.
Trong bng h thng tun hon (HTTH), s TT nguyn t = in tch ht nhn = s e.
VD: Ca c s TT= 20 => Z=s e=20.
2. Thuyt lng t
nh sng l mt sng in t lan truyn trong chn khng vi vn tc c = 3.108m/s, c
c trng bng bc sng hay tn s dao ng: =
Thuyt sng ca nh sng gii thch c nhng hin tng lin quan vi s truyn sng
nh giao thoa v nhiu x nhng khng gii thch c nhng d kin thc nghim v
s hp th v s pht ra nh sng khi i qua mi trng vt cht.
Nm 1900, M.Planck a ra gi thuyt: Nng lng ca nh sng khng c tnh cht
lin tc m bao gm tng lng ring bit nh nht gi l lng t. Mt lng t ca nh
sng (gi l phtn) c nng lng l:
E=h
Trong : E l nng lng ca photon
: tn s bc x
h = 6,626 .10-34 J.s - hng s Planck.
Nm 1905, Anhstanh da vo thuyt lng t gii thch tha ng hin tng
quang in. Bn cht ca hin tng quang in l cc kim loi kim trong chn khng
khi b, khi b chiu sng s pht ra cc electron; nng lng ca cc electron khng
ph thuc vo cng ca nh sng chiu vo m ph thuc vo tn s nh sng.
Anhstanh cho rng khi c chiu ti b mt kim loi, mi photon vi nng lng h s
truyn nng lng cho kim loi. Mt phn nng lng E0 c dng lm bt electron
ra khi nguyn t kim loi v phn cn li s tr thnh ng nng
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1 2
mv ca electron:
2
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h = E0 +
1 2
mv
2
Nhng bc x c tn s b hn tn s gii hn 0 =
E0
s khng gy ra hin tng
h
quang in.
S dng cng thc trn ta c th tnh c vn tc ca electron bt ra trong hin tng
quang in.
3. Cc m hnh nguyn t:
* M hnh nguyn t Rutherford: Mi nguyn t c mt ht nhn mang in tch dng
v cc e quay xung quanh.
* M hnh nguyn t Bohr:
- Trong nguyn t mi electron quay xung quanh nhn ch theo nhng qu o trn
ng tm c bn knh xc nh.
- Mi qu o ng vi mt mc nng lng xc nh ca electron. Qu o gn nhn
nht ng vi mc nng lng thp nht, qu o cng xa nhn ng vi mc nng
lng cng cao. Nng lng ca electron trong nguyn t H2 c xc nh nh sau:
En
1 me 4 1
.
.
=
8 20 h 2 n 2
Trong h = 6,626 .10-34 J.s - hng s Planck

m - khi lng ca e
o - hng s in mi trong chn khng o = 8,854.10-12 C2/Jm
n - l cc s nguyn dng nhn cc gi tr 1,2,3...,,
-
Khi e chuyn t qu o ny sang qu o khc th xy ra s hp th hoc gii phng

nng lng. Khi e chuyn t qu o c mc nng lng thp sang mc nng lng
cao hn th n hp th nng lng. Khi electron chuyn t mt mc nng lng cao
sang mc nng lng thp hn th xy ra s pht x nng lng. Nng lng ca bc
x hp th hoc gii phng l:
E = En - En = h = h.
* Kt qu v hn ch ca thuyt Bohr
Kt qu :
- Gii thch c quang ph vch ca nguyn t hyro
- Tnh c bn knh ca nguyn t hydro trng thi c bn a= 0,529 A0
Hn ch
- Khng gii thch c cc vch quang ph ca cc nguyn t phc tp
- Khng gii thch c s tch cc vch quang ph di tc dng ca in trng, t

trng
- Gi thuyt c tnh c on.
* Cc m hnh trn u khng gii thch c 1 s vn thc nghim t ra. Nguyn
nhn l do:
- Khng cp n tnh cht sng ca electron
- Do coi qu o chuyn ng ca electron trong nguyn t l qu o trn c bn
knh xc nh.
II. Quan im hin i v cu to nguyn t:
1. Lng tnh sng ht ca cc ht vi m

Nm 1924 nh vt l hc ngi Php Louis De Broglie a ra gi thuyt: mi ht
vt cht chuyn ng u c th coi l qu trnh sng c c trng bng bc sng
v tun theo h thc :
=
h
mv
Trong : m - Khi lng ca ht, kg

v - Vn tc chuyn ng ca ht , m/s
h - Hng s Planck, h= 6,63.10-34J.s
-
i vi ht v m: m kh ln (h =const) kh nh -> tnh cht sng c th b

qua.
i vi ht vi m : m nh (h =const) kh kh ln -> khng th b qua tnh cht

sng.
V d 1: Mt ht c khi lng m = 0,3 kg, vn tc chuyn ng V= 30m/s th ca
ht l?
Gii:
p dng h thc Louis De Broglie
h
6,63.10 34
=
= 0,736.10 34 m
mv
0,3.30
ca ht v cng nh nn b qua tnh cht sng ca ht.

2. Nguyn l bt nh Heisenberg
* Pht biu nguyn l
Khng th xc nh ng thi chnh xc c to v vn tc ca ht, do khng th
v c chnh xc qu o chuyn ng ca ht.
x. vx
h
m
y l h thc bt nh Heisenberg
Trong x- bt nh (sai s) v to theo phng x
vx- bt nh (sai s) v vn tc theo phng x

Nu x cng nh th vx cng ln, ngha bt nh v to cng nh th bt
nh v vn tc cng ln.
T y rt ra mt kt lun quan trng l khng th dng c hc c in m t mt
cch chnh xc qu o chuyn ng ca ht vi m nh thuyt ca Bohr m phi s
dng mt mn khoa hc mi l: c hc lng t.
III. Khi nim v c hc lng t
1.Hm sng:
Trng thi chuyn ng ca e trong nguyn t c m t bng mt hm ca to
x,y,z v thi gian t, c gi l hm sng (x,y,z,t).
Trong trng hp t khng i th khng ph thuc vo thi gian, c gi l trng
thi dng ca electron. Khi ch ph thuc vo 3 bin x,y,z.
* Tnh cht ca hm sng:
- C th l m, dng hay l 1 hm phc.
- 2 mt xc sut tm thy electron ti 1 im trong phn khng gian xung quanh
ht nhn.
-
2dv m t xc sut tm thy electron thi im t trong yu t th tch dv bao

quanh im c to x,y,z
V electron c mt trong khng gian v hn nn xc sut tm thy n bng 1:
+
dv = 1 L iu kin chun ha hm sng.
2. Phng trnh Schrodinger:

tm ra hm sng ta phi gii phng trnh sng, cn gi l phng trnh
Schrodinger. l phng trnh vi phn ca hm sng i vi ht vi m (eleclectron)
chuyn ng trong trng th V:
h2

+ V = E
2
8 m
Trong d: =
2
2
2
- Ton t Laplace
+
+
x 2 y 2 z 2
V- L th nng ca ht
E - Nng lng ton phn ca ht
C th vit di dng tng qut hn: H=E, trong H l ton t Hamilton ca h
nghin cu.
Gii phng trnh sng tm c E, t bit c chuyn ng ca e.
3. Obitan nguyn t v my electron.

-
Mi gi tr nghim gi l 1 obitan nguyn t, k hiu l AO.

My e c quy c l min khng gian gn ht nhn nguyn t, trong xc sut c
mt electron khong 90%. Mi m my electron c xc nh bng mt b mt gii
hn gm nhng im c cng mt xc sut. m my s l hnh cu. m my p
c dng hnh qu t i, m my d c dng hnh hoa bn cnh.
y
x
y
x
dx2-y2
y
x
x
z
dxz
y
x
dxy
dyz
IV. H 1 e ( nguyn t H v ion tng t).
1. Phng trnh sng:

- H gm 1 e v 1 ht nhn in tch +Ze:
Th nng ca h:
V=
Ze 2
4 0 r
Trong r: khong cch gia ht nhn v e.

0 : hng s in mi ca chn khng.
th nng V ch thuc vo r => trng to ra l trng xuyn tm ( trng c i

xng tm) gi l trng Culng.
Phng trnh Schrodinger c dng:
h2
Ze 2

2
4 0 r
8 m
= E
gii phng trnh sng trn a v h ta cu: (x,y,z) (r,,)
Li gii phng trnh sng Schrodinger s thu c l nng lng ton phn ca e
(E), hm sng m t trng thi chuyn ng ca e () v khi gii s xut hin 3 s
lng t n, l ,m.
2. Nng lng:
* Kt qu gii phng trnh sng thu c nng lng ton phn ca e:
E n = 13,6.
z2
(eV)
n2
n: c gi tr nguyn dng, gi l s lng t chnh.

* Nhn xt:
- Ee ph thuc vo n
+ n cng ln -> Ee cng ln v ngc li.
+ n gin on Ee gin on -> nng lng ca e trong nguyn t c phn
thnh tng mc, mi mc ng vi 1 gi tr ca n.
+ Khi n=1 E1 min -> mc E1 gi l trng thi c bn. Vy trng thi c bn l
trng thi c mc nng lng thp nht.
3. Hm sng:
(x,y,z) = (r,,)
-
Khi gii phng trnh sng, dn n vic t hm sng (r,,) thnh tch ca hai
hm:
(r,,)= Rn,l (r).Ym,l(,)

Trong : R(r)
- L hm xuyn tm ph thuc vo hai tham s n, l
Y (,) - L hm gc ph thuc vo hai tham s l l, m.

l - l s lng t ph :
l = 0,1,2,...,n-1 -> ng vi 1 gi tr ca n c n gi tr
m - l s lng t t :
m = 0, 1,2,...,l -> ng vi 1 gi tr ca l c
ca l.
2l + 1 gi tr ca m.
-
Nh vy hm sng thu c ph thuc vo 3 s lng t l n,l,m : n,l,m hay ni
cch khc: Mt hm sng (1AO) c c trng bng 3 s lng t n,l,m.

* Nhn xt:
- Cc e c cng 1 mc nng lng c th c n trng thi khc nhau, mi trng thi
c c trng bi s lng t l.
- ng vi mi 1 trng thi c th c 2l+1 cch nh hng khc nhau trong khng gian.
VD: n=1 ( mc nng lng K) -> l =0, m=0 => n,l,m= 100
100 =1AO => mc nng lng K c 1 AO.
n=2 (mc L) l =0,1; m=0, 1.
n =2, l =0 => 200=1AO.

n =2, l =1 => m=0
=> 210=1AO.
m=1
=> 211=1AO.
m=-1
=> 21-1=1AO.
Mc L c 4 AO
Vy: Mt mc nng lng n c n2 hm sng => c n2 AO.
Mt gi tr ca l c (2l+1) hm sng -> c (2l+1) AO
4. Gii thiu mt s my e
Hnh dng ca cc my e gn ging hnh dng ca cc AO tng ng nhng ch khc:
khi biu din hm sng th c du (+) hay (-) cn my e th khng c du.
Gi tr ca l:
0
1
2
3
K hiu:
s
p
d
f
Vy vi
n 1 => c ns = AO ns => my ns.

n 2 => c np = AO np => my np.
m=0 (z) -> np = AO npz => my npz
z
m=1 (x) -> np = AO npx=> my npx

x
m=-1 (y) -> np = AO npy => my npy.

y
My np gm 3 m my ng vi 3 gi tr ca .
a. My ns
-
ns c tnh cht i xng cu, khng ph thuc vo , .
My s: Mt my e phn b ng hng v l 1 khi cu.

z
x
y
x
y
My s
AO ns
b. My p
-
Mi hm ns l 2 mt cu i xng nhau qua gc ta c phn (+) v phn (-) theo
chiu ca trc ta .
Mi my p: C dng hnh qu t, cc i ca my e phn b dc theo trc ta .
5. Chuyn ng ring ca e trong nguyn t:

Chuyn ng ton b ca e trong nguyn t gm 2 chuyn ng:
Chuyn ng xung quanh nhn ( chuyn ng obitan) c c trng bng 3 s

lng t n,l,m.
- Chuyn ng ring(chuyn ng t quay) c c trng bng s lng t t spin
ms; ms ch nhn 2 gi tr l +1/2 hoc 1/2.
* Vy chuyn ng ca ton b e trong nguyn t c c trng bi 4 s lng t
n,l,m v ms trong :
- n c trng cho kch thc my e.
- l c trng cho hnh dng my e.
- m c trng cho hng my e.
V. H nhiu e
H nhiu e -> e kho st chu tc dng ca:

- Lc ht ht nhn.
- Lc y ca cc e cn li.
trng th to ra khng xuyn tm, nng lng ca e trong trng ny khng
nhng ph thuc vo n m cn ph thuc vo l. kho st h ny -> phi a
h v h 1e -> dng phng php gn ng.
1. Phng php gn ng 1e. Khi nim in tch ht nhn hiu dng
* Phng php gn ng 1e:
- Coi e kho st chuyn ng trong 1 trng Z do ht nhn v tt c cc e cn li gy
ra. Z c gi l in tch ht nhn hiu dng.
- Z = Z- A, A l hng s chn ca cc e cn li.
- Coi cc e cn li chn bt nh hng ht nhn 1 i lng A
- Coi trng to ra do Z l trng xuyn tm.
* Kt qu ca bi ton 1 e c th p dng cho bi ton nhiu e ( bng cch s dng
phng php gn ng trn): Cc biu thc tnh E, u ging nhau, ch khc ch no
c Z th c thay th bng Z.
2. p dng kt qu bi ton 1e cho h nhiu e.
a. Nng lng:
- H 1 e : E n = 13,6.
-H nhiu e: E n,l
Z2
n2
Z' 2
= 13,6. 2
n
=> E=f(n).
=> E=f(n,Z) =f(Z,n,l).
Nhn xt:
- Vy trong h 1 e => E ch ph thuc vo s lng t chnh n, cn trong h nhiu e th
E ph thuc vo n v Z (hoc Z, n v l).
- Trong h nhiu e, mt mc nng lng b tch thnh n phn mc, mi phn mc c
trng bi 1 gi tr ca l.
l c trng cho lc y ca cc e cn li, l cng ln En,l cng ln.

Trong h nhiu e, nng lng c hin tng suy bin.
b.Hm sng
Hnh dng AO v my e hon ton khng i (nh trong h 1e) nhng mt phn b e
theo khong cch ti nhn l khc nhau do Z Z.
3. ngha ca 4 s lng t:
*Khi nim lp, phn lp e:
- Lp e: Trong nguyn t nhiu electron, nhng electron c cng gi tr s lng t
chnh to thnh mt lp. Cc lp c k hiu nh sau:
n
Lp
1
K
2
L
3
M
4
N
5
O
6
P
7
Q
n cng ln th lp electron cng xa nhn v electron c nng lng cng cao.

- Phn lp e: Trong cng mt lp cc electron c chia thnh n phn lp, mi phn
lp trong cng mt lp c c trng bng mt gi tr ca l. k hiu cc phn
lp dng cc k hiu sau y:
l
0
1
2
3
K hiu s
p
d
f
ch phn lp electron thuc lp no vit thm h s c gi tr bng s lng t
chnh n ca lp trc k hiu phn lp.
V d:
Lp K ng vi n = 1 ch gm c mt phn lp c c trng bi l = 0 v n=1, 1s
l = 0 2s
l = 1 2p
Lp L ng vi n=2 gm c hai phn lp c c trng
l = 0 3s
Lp M ng vi n=3 gm c 3 phn lp c c trng l = 1 3p

l = 2 3d
ngha ca 4 s lng t:
a. S lng t chnh n.
- Xc nh lp e trong nguyn t
VD: n =1 -> ng vi lp K
n=2-> ng vi lp L
- Xc nh kch thc ca my e: n cng ln -> kch thc my e cng ln v mt
my e cng long.
i vi nguyn t H hay ion 1 e, n xc nh mc nng lng ca e trong nguyn t

hoc ion: E n = 13,6.
Z2
n2
i vi nguyn t nhiu e -> Ee =f(n,l) n ch xc nh mc nng lng trung bnh

ca cc e trong cng 1 lp: E n,l
Z' 2
= 13,6. 2
n
b. S lng t ph l
- xc nh hnh dng ca m my e
My s hnh cu, my p - qu t i, my d dng phc tp.
c. S lng t t:
- m xc nh s nh hng ca AO hay cc my electron trong khng gian xung
quanh ht nhn.
V d: ng vi l=0 (my s) => m=0; my s ch c 1 s nh hng xung quanh
ht nhn (my s c hnh cu).
l=1 (my p) => ma= -1, 0 ,+1 my p c 3 s nh hng khc nhau xung quanh
ht nhn.
d. S lng t t spin ms: c trng cho s chuyn ng ring ca e.
VI. S phn b e trong nguyn t nhiu e.
1. Nguyn l ngoi tr Pauli

Trong mt nguyn t khng th tn ti hai electron c cng gi tr ca 4 s lng t.
1
2
VD: Lp K; n=1 => l=0 => m=0=> ms =+ v ms =-
1
2
1
2
lp K c nhiu nht 2 e: e th nht c ga tr n =1, l=0, m =0 v ms =+ ; e th 2

c gi tr n =1, l=0, m =0 v ms=-
1
2
H qu: Da vo nguyn l pauli c th tnh c s electron ti a trong mt lng

t, mt phn lp hay mt lp.
+ S electron ti a trong mt lng t l 2e (v trong mt lng t cc e c 3 s
lng t ging nhau, s lng t th t ms phi khc nhau, nhn gi tr l +1/2 v -1/2)
+ S electron ti a trong mt phn lp l 2(2l+1).
Phn lp
s
p
d
f
S lng t
1
3
5
7
2
6
10
14
S e ti a
VD: Tnh s e ti a phn lp np ( n c gi tr bt k).
VD n =2, cn p ng vi l=1. T :
n=2 -> l=1 => m=-1 => ms=+1/2 v ms=-1/2 => ng vi AO 2py c nhiu nht 2e.
n=2 -> l=1 => m=0 => ms=+1/2 v ms=-1/2 => ng vi AO 2pz c nhiu nht 2e.
n=2 -> l=1=> m=+1 => ms=+1/2 v ms=-1/2 => ng vi AO 2px c nhiu nht 2e.
Vy phn lp p c nhiu nht 6e.
- S e nhiu nht cc phn lp: Mt lp e ng vi 1 gi tr ca n c ti a 2n2 e.
VD: Tnh s e ti a lp L ( n=2).
n=2 -> l=0 => m=0 => ms=+1/2 v ms=-1/2 c ti a 2e.
l=1 => m =-1 => ms=+1/2 v ms=-1/2 c ti a 2e.
m=0 => ms=+1/2 v ms=-1/2 c ti a 2e.
m=+1 => ms=+1/2 v ms=-1/2 c ti a 2e.
Vy lp L (n=2) c nhiu nht l 8e=2n2.
2. Nguyn l vng bn:
Trong nguyn t cc electron chim trc ht cc AO c mc nng lng thp nht .
Nng lng ca cc AO trong nguyn t c xp theo th t tng dn nh sau:
1s < 2s < 2p < 3s < 3p < 4s 3d < 4p < 5s 4d < 5p < 6s < 4f 5d < 6p < 7s
Tha mn quy tc Klechkowsky:
3. Quy tc Hund
- lng t: Mi AO c c trng bng 3 s lng t n,l, m; mi AO c biu
din bng 1 vung c gi l 1 lng t, k hiu l
- Quy tc Hund: Trong mt phn lp cha s electron ti a cc electron c khuynh
hng phn b u vo cc lng t sao cho s electron c thn vi spin song
song l cc i.
* Quy lut phn b cc e trong nguyn t: phi tun theo nguyn l Pauli, nguyn l
vng bn v quy tc Hund.
4. Cch vit cu hnh e ca nguyn t trng thi c bn.
a. Cu hnh dng ch:

* vit cu hnh e dng ch cn bit:
- S e trong nguyn t (bng Z).
- Th t in cc electron theo nguyn l vng bn .
- Bit s electron ti a trong mt phn lp: Phn lp s c ti a 2e, phn lp p - 6e,
phn lp d - 10e, phn lp f- 14e.
* Cch vit:
- Vit di dng k hiu cc phn lp.
- in e theo th t nng lng tng dn v cc e mi phn lp vit di dng s m
( tng tt c cc s m cc phn lp = s e = Z).
VD: Vit cu hnh e nguyn t ca Mn (Z=25) dng ch.
Mn (Z=25) -> s e = 25 : 1s22s22p63s23p64s23d5
Hay: 1s22s22p63s23p63d54s2
* Ch : - Khi vit cu hnh e ca nguyn t th s e =Z nhng khi vit cu hnh e ca ion
th phi ch s e s Z (in tch ht nhn ca ion v nguyn t nh nhau nhng s e
th phikhc nhau): S e < Z ( i vi ion dng) v s e > Z ( i vi ion m).
VD: Mn3+ (Z=25) -> s e =22: 1s22s22p63s23p63d4.
Vit cu hnh e ca nguyn t hay ion: khi in e vo nguyn t lun in theo th t
nng lng theo nguyn l vng bn nhng khi mt e ( tr thnh ion) th mt e lp
ngoi cng trc ( mt t lp ngoi ri ti lp trong) : in (n-1)d sau ns, khi mt ns
trc (n-1)d.
6. Cu hnh e nguyn t dng lng t:
* Cch vit:
- Vit cu hnh e dng ch.
- Da vo cu hnh e dng ch vit cu hnh e dng lng t ( mi lng t cha
ti a 2e).
- Mi e c k hiu bng 1 mi tn quay ln (vi ms=+1/2) , quay xung quay ln (
vi ms=-1/2).
=> 2e ghp i,
- Nu 1 c 2e -> 2e phi c spin ngc chiu nhau
spin =0. Nu 1 c 1e
-> gi l e c thn.
- Vi nhng phn lp cha bo ha e-> vic fn b e phi tun theo quy tc Hund.
VD: Vit cu hnh e di dng ca N (z=7)
N(Z=7) 1s22s22p3
* Ch : Trong mt s nguyn t, vit cu hnh e theo nguyn l vng bn trng thi

c bn c cu hnh ns2(n-1)d4 hoc ns2(n-1)d9 th c s chuyn 1e ns sang (n-1)d thnh
ns1(n-1)d5 hoc ns1(n-1)d10. Nguyn nhn l do hiu nng lng (E(n-1)d- Ens) nh v cc
phn lp d10 v d5 l cc phn lp bo ha v na bo ha l cc phn lp bn => khi
(n-1)d c s e gn bng 10 (hoc gn bng 5) th 1 e ns s chuyn sang (n-1)d to
thnh cc phn lp bn.
Chng II
NH LUT TUN HON - BNG TUN HON CC NGUYN T
HO HC
I. M u
Nm 1869, Mendeleep khm ph ra nh lut tun han : Tnh cht ca cc

nguyn t v hp cht ca chng bin thin tun hon theo chiu tng ca khi lng
nguyn t. Trn c s Mendeleep xp 63 nguyn t thnh bng tun hon
(HTTH) theo chiu tng ca khi lng nguyn t.
Vi cch sp xp cho php suy on s xut hin cc nguyn t mi nhng cn mt
s hn ch:
- Khng gii thch c nguyn nhn ca tnh tun hon.
- Khng gii thch c s khc nhau v s nguyn t gia cc hng.
- C trng hp ngoi l, khi lng nguyn t ca nguyn t ng trc ln hn
khi lng nguyn t ca nguyn t ng sau.
Ar(Z=18): 39,948 > K (Z= 19) : 39,698
Co (Z=27): 58,933> Ni(Z=28): 58,70
Te (Z= 52): 127,60> I (Z=53): 126,9015
II. nh lut tun hon. HTTH theo thuyt cu to hin i.
Ngy nay, di nh sng ca thuyt cu to nguyn t, nh lut tun hon v HTTH l

h qu t nhin ca cc quy lut tun hon trong cu to v e ca cc nguyn t.
1. nh lut tun hon:
Tnh cht ca cc nguyn t v hp cht ca chng bin thin tun hon theo chiu tng
ca in tch ht nhn.
Tnh tun hon l do s bin i tun hon trong cu to ca cc nguyn t theo chiu
tng ca in tch ht nhn. => Tnh cht nguyn t v hp cht ca chng do in tch
ht nhn quyt nh.
2. Bng tun hon cc nguyn t ha hc
th hin c tnh tun hon trong cu to nguyn t v tnh cht cu cc nguyn t > xp cc nguyn t thnh HTTH theo nguyn tc sau:
* Nguyn tc xp:
- Xp theo chiu tng dn ca in tch ht nhn.
- m bo tnh tun hon v cu hnh e nguyn t ca cc nguyn t.
+ Cc nguyn t c cng s lp e xp theo 1 hng (chu k).
+ Cc nguyn t c s e lp ngoi cng ging nhau hoc 2 phn lp e ngoicng
ging nhau c xp vo 1 ct.(nhm)
a. Chu k: L tp hp cc nguyn t c cng s lpv e v t theo 1 hng ngang.
- S lp e = s th t chu k.
Gm 7 hng ngang ng vi 7 chu k, khng phn bit chu k ln nh, chn l:

Chu k 1: Ch c 2 nguyn t (xy dng phn lp 1s)
Chu k 2, 3: Mi chu k c 8 nguyn t (xy dng cc phn lp 2s, 2p, 3s, 3p)
Chu k 4, 5: Mi chu k c 18 nguyn t
Chu k 6: C 32 nguyn t
Chu k 7: Cn ang d dang.
* Nhn xt: - Trong 1 chu k i t u ti cui chu k, s e lp ngoi cng tng dn t 1>8.
- S bin thin tun hon trong cu to nguyn t ca cc nguyn t khng lp li 1 cch
n gin m c s m rng t chu k 4 -> s nguyn t trong cc chu k tng.
b. Nhm: L tp hp cc nguyn t c cu hnh e ha tr tng t nhau xp thnh mt
ct.
Gm 8 nhm: nh s t I->VIII, mi nhm c chia thnh 2phn nhm:
* Nhm A(phn nhm chnh): Nguyn t ca cc nguyn t nhm A c c im:
- Nguyn t ang c in e vo phn lp ns hoc np ( n l lp ngoi cng).
- VD: Z=3; 1s22s2
Z= 9 1s22s22p5
- S e lp ngoi cng ca nguyn t = s th t nhm cha n.
- nhn bit 1 nguyn t thuc nhm A no -> da vo cu hnh e nguyn t:
Nhm IA: gm cc nguyn t c cu trc e lp ngoi cng l ns1
Nhm IIA:
ns2
Nhm IIIA:
ns2np1
Nhm IVA:
ns2np2
Nhm VA:
ns2np3
Nhm VIA:
ns2np4
Nhm VIIA:
ns2np5
Nhm VIIIA:
ns2np6
Nhm B( phn nhm ph): Nguyn t ca cc nguyn t nhm B c c im:
- Nguyn t ang c in e vo phn lp (n-1)d hoc (n-2)f
VD Z=21 : 1s22s22p63s23p64s23d1 => thuc nhm B
- S e lp ngoi cng ca hu ht cc nguyn t nguyn t nhm B l 2 (ns2), ca mt
s t l 1 (ns1) v ca 1 trng hp Pd (Z=46) khng cha e no lp ngoi cng
(5s0). Vy s e lp ngoi cng ca cc nguyn t nguyn t nhm B < 3=> hu ht
cc nguyn t nhm B l kim loi.
- nhn bit 1 nguyn t thuc nhm B no -> da vo cu hnh e nguyn t:
Nhm IIIB:
c hai phn lp ngoi cng l (n-1)d1ns2
Nhm IVB:
Nhm VB:
Nhm VIB:
c hai phn lp ngoi cng l (n-1)d4ns2 (n-1)d5ns1
Nhm VIIB:
Nhm VIIIB:
c hai phn lp ngoi cng l (n-1)d6,7,8ns2
Nhm IB:
Nhm IIB:
* Nhn xt:
+ Nu vit cu hnh e nguyn t da vo dy nng lng theo nguyn l vng bn => th
tt c cc nguyn t nhm B u c 2 e lp ngoi cng ns2. Tuy nhin thc nghim xc
nh rng 1 s nguyn t nguyn t nhm B c 1 e ns -> (n-1)d, tr 1 trng hp Pd
2e 5s2 u chuyn vo 4d. Cc trng hp ny xy ra khi phn lp (n-1)d gn na bo
ho (d5) hoc bo ha (d10) l cc phn lp bn v nng lng e phn lp (n-1) v ns xp
x nhau.
+ Cu hnh e nguyn t ca 1 s nguyn t m s in e cui cng xy ra (n-2)f cng
hi khc so vi cch in e theo nguyn l vng bn.
VD Z=64:
1s22s22p63s23p64s23d104p65s24d105p66s24f8 ( theo nguyn l vng bn)
Trong thc t: 1s22s22p63s23p64s23d104p65s24d105p66s24f75d1.
1e 4f chuyn sang 5d: t ti cu hnh bo ha na s e f7 bn.
* Nguyn t s, p, d, f:
- Nguyn t m s in e cui cng vo nguyn t xy ra ns gi l cc nguyn t s.
nh ngha tng t i vi cc nguyn t p, d,f.
+ Cc nguyn t nhm IA, IIA l cc nguyn t s.
+ Cc nguyn t nhm IIIA->VIIIA l cc nguyn t p.
+ Cc nguyn t nhm B l cc nguyn t d (ring nhm IIIB c c nguyn t f).
+ Cc nguyn t f m s in e cui cng vo nguyn t xy ra 4f -> gi l cc
nguyn t lantanoit hoc cc nguyn t h lantan, cn cc nguyn t f m s in e cui
cng 5f -> cc nguyn t Actinoit (h actini).
3. Mt s dng bng HTTH
a. Dng bng ngn
- Chu k nh c 1 hng, chu k ln c 2 hng.
- C 8 nhm, mi nhm chia thnh 2 phn nhm : phn nhm chnh (A) v phn nhm
ph (B).
b. Dng bng di:
- Cc nguyn t trong mi chu k c xp thnh 1 hng.
- Ton bng c 16 nhm, nh s t IA, IIA...VIIIA v IB,IIB.. VIIIB. H lantan v h
actini gm cc nguyn t f c xp vo nhm IIIB.
III. S bin i tun hon 1 s tnh cht ca cc nguyn t
1.Hiu ng chn:
Trong nguyn t H c 1 e -> e ny b ton b in tch ht nhn ht
Trong nguyn t nhiu e, ngoi lc ht ca ht nhn i vi cc e, cn lc y gia cc e
c in tch cng du. Lc y ny lm gim lc ht ca ht nhn i vi cc e. Trong
trng hp ny ngi ta ni cc e chn ln nhau. Nh vy trong nguyn t nhiu e, mi e
u b chn bi cc e cn li v chnh n li chn cc e khc trong nguyn t nhng s
chn ny khng hon ton.
n 1
A = Ai
A: H s chn tng cng ca cc e cn li i vi e xt.
i =1
n: s e c trong nguyn t.
Ai: H s chn ca e th i i vi e kho st.
V chn khng hon ton => Ai <1.
Khi A tng ->tc dng chn ca e th i i vi e kho st tng v Z i vi e kho st
gim v ngc li.
* Nhn xt v quy lut chn:
- Cc e cng xa nhn ( cc e c n ln v l ln) th b chn cng nhiu v tc dng chn
ca n i vi e cng t ( e xa nhn nht l e c gi tr n v l ln nht).
- Cc e trong cng 1 lp (cng n) chn ln nhau km v theo chiu ns-np-nd-nf tc
dng chn gim dn, kh nng b chn tng dn (A tng).
- Cc e trong cng 1 phn lp ( cng n,l) chn ln nhau cng km, c bit cc e trong
cng 1 phn lp y 1 na, s e c spin song song nhau chn ln nhau km nht ( v
lc ny mi e chim 1 AO trong phn lp xa nht).
- Cc phn lp bo ha e thuc lp bn trong mt e dy c chn mnh e bn ngoi.
2. Quy lut bin thin nng lng ca cc AO ha tr EAO
Theo cng thc:
EAO ha tr =
2
(
Z A)
13,6
n2
Z'2
= 13,6 2
n
khi Z tng th EAO gim.

n tng -> EAO tng.
a. Trong 1 chu k
- Trong 1 chu k, t tri qua phi EAO ha tr gim v n=const, Z tng -> Z tng: Z tng
do A tng chm hn Z, A tng chm v t tri qua phi trong 1 chu k cc e c in
vo cng mt lp nn tcdng chn ln nhau km (s nh).
- Trong mt chu k t tri qua phi, hiu nng lng gia cc AO np v ns tng dn:
E = E np E ns tng .
b. Trong 1 nhm: t trn xung trong 1 nhm th:
EAO ha tr tng dn do:

+ Z tng nhiu t 8-> 18, cu trc bo ha e chn mnh vi e ngoi => Z tng chm
hn, n tng nhanh hn.
- Hiu E = E np E ns gim do n tng nhanh.

3. Nng lng ion ha ca nguyn t I (eV, kJmol-1)
a. Nng lng ion ha th nht: I1
Nng lng ion ho th nht I1 l nng lng ti thiu cn thit tch 1e ra khi
nguyn t trng thi c bn v th kh thnh ion tch in +1 cng trng thi kh v
c bn.
X(K,CB) - 1e X+(K,CB)
I1 > 0, I1- l nng lng ion ho th nht
Nng lng ion ho th hai ng vi qu trnh bt electront h hai

X+(K,CB) - 1e X2+(K,CB)
I2 > 0
Ta lun c I2 > I1
b. Electron no b tch khi nguyn t khi b ion ha:
Khi nguyn t b ion ha th e lin kt yu nht vi ht nhn s b bt ra trc tin, l
e lp ngoi cng (ng vi e c n ln nht) c nng lngln nht.
VD Ti (Z=22) 1s22s22p63s23p64s23d2
e lp ngoicng l 4s2 -> cc e ny b tch trc tin khi b ion ha, sau mi
n cc e 3d2.
c. Cc yu t nh hng n nng lng ion ho:

Khi nguyn t mt e tc l xy ra hin tng ion ho th e s chuyn t cc AO ra xa
v cng. Khi nng lng ion ho ng vi qu trnh mt e c tnh bng cng thc:
I = E - Ee = 13,6.
Z' 2
(eV)
n2
Trong : E l nng lng ca electron xa v cng = 0

Ee l nng lng ca electron b tch
T biu thc ta thy rng nng lng ion ho I ph thuc vo n v Z. I cng ln khi n
nh v Z ln. Z ph thuc vo Z v A do I s ph thuc vo n, l v Z.
d. Quy lut bin i I1 trong 1 chu k:
Trong mt chu k khi i t tri sang phi ni chung I1 tng dn v t gi tr cc i
kh tr. T nguyn t kh tr ca chu k trc n nguyn t u tin ca chu k tip
theo I1 li gim xung t ngt ri li tng dn nh chu k trc. Qu trnh lp i lp li
t chu k ny sang chu k khc v c gi l s tun hon ca I1.
Gii thch: Trong 1 chu k, t tri qua phi th Ee gim -> I1 tng do n=const , Z tng
dn (Z tng mnh hn A).
I1 min u chu k ns1
I1 max cui chu k ns2np6
V vi ns1 lp bn trong bo ha-> chn tt-> I1 min.
ns2np6 bo ha -> kh tch e ->I1 max.
V n = const Z tng dn, tuy nhin I1 tng khng u v thy xut hin nhng cc
tiu nh (bn trong mt chu k) nhng nguyn t c phn lp ngoi cng c phn
b y (ns2) hoc y mt na electron (np3).
I1
He
Ne
N
F
Be
B
H
Ar
C O
P
Cl
Mg
Si S
Li
Na
Al
Z
Cc cc tiu nh xut hin bn trong mi chu k, nn y l s tun hon ni chu k
ca nng lng ion ho th nht.
Trong mt phn nhm chnh khi i t trn xung gi tr I1 gim dn, cn trong mt
phn nhm ph s bin thin ny chm v khng u.
e. Quy lut bin i I1 trong nhm:
Trong mt phn nhm chnh khi i t trn xung gi tr I1 gim dn, cn trong mt
phn nhm ph s bin thin ny chm v khng u.
4. i lc i vi e ca nguyn t A (eV,kJ)
L kh nng kt hp electron ca nguyn t to thnh ion m, n ng vi qu trnh:
X(k,cb) + 1e -> X-1(k,cb)
Vy: Nng lng kt hp electron l nng lng thot ra hay thu vo khi kt hp
thm 1e vo nguyn t trung ho trng thi kh, c bn.
- Khc vi nng lng ion ho th nng lng kt hp electron c th m, dng hoc
bng 0. i lc vi electron cng ln th nng lng kt hp electron cng nh.
- Trong mt chu k i lc vi electron tng dn v t cc i cc nguyn t nhm
VIIA
5. m in ca nguyn t ( )
nh ngha: l i lng c trng cho kh nng ht cp e lin kt ca nguyn t trong

phn t.
-
Cng thc tnh theo phng php Miliken:

=
I X + AX
2
Ix,AX: nng lng ion ha v i lc e ca nguyn t X.

Tng (Ix+AX) cng ln => kh nng ht e ca nguyn t cng ln.
6. Tnh kim loi v phi kim:
- Tnh kim loi: L tnh d nhng electron
Mt nguyn t c s e lp ngoi cng < 4 l kim loi tr B (Z = 5) v H (Z=1), l
cc nguyn t nhm IA, IIA, IIIA. Mt s nguyn t kim loi c s e lp ngoi cng l 4
nh Ge, Sn, Pb; c s e ho tr l 5 nh Bi, Sb.
- Tnh phi kim: L tnh d nhn e
Cc nguyn t c s e lp ngoi cng > 3 l nguyn t phi kim
l cc nguyn t nhm IVA, VA, VIA, VIIA tr Sn, Pb, Ge (IVA), Sb, Bi(VA) l
cc kim loi.
- Quy lut bin i:
Trong mt chu k khi i t u n cui chu k tnh kim loi gim dn, cn tnh phi
kim tng dn.
Trong mt phn nhm chnh t trn xung tnh kim loi tng dn cn tnh phi kim
gim dn. Trong phn nhm ph i t trn xung tnh kim loi gim dn.
7. S xi ha ca nguyn t
Khi tng tc ho hc lun xy ra s di chuyn electron ho tr t nguyn t ny sang
nguyn t khc. Chnh s di chuyn ny xc nh s oxi ho ca nguyn t tham gia
tng tc.
Nguyn t mt e ho tr s tch in dng v do n s c s oxi ho (+). S oxi
ho (+) = s e ho tr mt. Nguyn t thu e ho tr s tch in m, do c s oxi ho
(-). Nh vy, s oxi ho = s e ho tr nhng hoc nhn.
S oxi ho cao nht ca mt nguyn t = s th t nhm ca n tr F, O, cc nguyn
t nhm IB, VIIIB.
S oxi ho m thng ch c cc nguyn t phi kim t IVA n VIIA. S oxi ho
m thp nht ca cc phi kim = s th t nhm - 8
V d: s oxi ho m thp nht ca cc halogen nhm VIIA l = 7-8 = -1
s oxi ho m thp nht ca cc nguyn t nhm VIA l = 6-8 = -2
s oxi ho cao nht ca cc nguyn t nhm VA, VB l +5
s oxi ho cao nht ca cc nguyn t nhm VIIA (tr F), VIIB l +7
IV. Mi lin h gia cu to nguyn t vi v tr v tnh cht ca cc nguyn t trong bng
tun hon
1. Bit cu to v electron suy ra v tr v tnh cht

V d 1: Nguyn t c Z = 22
Bit Z vit cu hnh electron: 1s22s22p63s23p63d24s2
- Lp ngoi cng c n= 4 nn nguyn t chu k 4
- Cc electron cui cng ang c in phn lp d nn l nguyn t d v thuc
nhm B
- Tng s e phn lp ns + s e phn lp (n-1)d = 4 nn nguyn t thuc nhm IVB

- V c s e lp ngoi cng = 2 < 4 nn l kim loi
V d 2: Nguyn t c Z = 35
Cu hnh electron ca nguyn t l: 1s22s22p63s23p64s23d104p5
- Nguyn t thuc chu k 4 v c 4 lp electron
- y l nguyn t p v cc e cui cng ang in phn lp 4p
- S e lp ngoi cng = 7 > 3 l phi kim, thuc nhm VIIA
2. Bit v tr trong bng tun hon suy ra cu to v electron
V d 1: Nguyn t X, chu k III, nhm VIIA
- V nguyn t chu k III nn c 3 lp electron
- V nhm VIIA nn cu trc lp e ngoi cng l ns2np5
- Cu hnh electron: 1s22s22p63s23p5
V d 2: Nguyn t A chu k IV, nhm VIIB
- V chu k IV nn c 4 lp v electron n = 4
- Nhm VIIB, cu trc lp v electron ngoi cng l: (n-1)d5ns2: 3d54s2
- Cu trc v electron: 1s22s22p63s23p63d54s2
CHNG III
LIN KT HO HC V CU TO PHN T
A - Lin kt ho hc
I. Cc c trng c bn ca lin kt ho hc
1. Nng lng lin kt (E):

( y quy c E ng vi qu trnh ph v lin kt)
Nng lng lin kt l nng lng ng vi qu trnh ph v lin kt, do nng
lng lin kt cng ln th lin kt cng bn.
i vi phn t 2 nguyn t, nng lng lin kt ng vi qu trnh:
A-B(K,CB) A(K,CB) + B(K,CB), EA-B> 0.
V d: HCl(K,CB) H(K,CB) + Cl(K,CB), EHcl = 431 kJ.mol-1
i vi phn t nhiu nguyn t kiu ABn, nh CH4 -> dng k hiu nng lng lin
kt trung bnh.
; H = 4 EC H
CH4(k,cb) -> C(k,cb) + 4H(k,cb)
1
4
=> EC H = H = 416 (kJ.mol-1)

2. di lin kt:
L khong cch gia hai tm ca hai nguyn t tham gia lin kt. di lin kt
thng c tnh bng nanomet (nm) hoc anstron (A0).
0
VD: lH-H= 0,74 A

=> l tng -> bn lin kt gim v ngc li.
3. Gc lin kt:
L gc to bi mt nguyn t lin kt trc tip vi hai nguyn t khc trong phn t.
V d: Oxy to hai lin kt vi hai nguyn t H trong phn t H2O. Gc lin kt HOH
trong phn t nc l 104,50
O
H
II. Phn loi lin kt
Da vo chnh lch v gia 2 nguyn t tham gia lin kt ( ).
1.Lin kt ion
- iu kin to thnh: Khi hai nguyn t tham gia lin kt c s chnh lch v m
in l 2. Khi cp e ho tr s chuyn hn t nguyn t c m in nh
hn sang nguyn t c m in ln hn, do s hnh thnh ra cc ion ngc du.
Sau cc ion ngc du s lin kt vi nhau bng lc ht tnh in ca cc ion
ngc du.
Vy bn cht ca lin kt ion l lc tnh in gia cc ion tri du.
xy ra bi 1 kim loi in hnh v 1 phi kim in hnh.
VD: Na 1e = Na+
Cl +1e =Cl hnh thnh lin kt ion trong NaCl.
c im lin kt:
- Lin kt ion khng c tnh nh hng: Mi ion c th to ra mt in trngxung

quanh n, do lin kt ion c hnh thnh theo mi hng
- Lin kt ion khng c tnh bo ho, v vy mi ion c th ht c nhiu ion xung
quanh n
- Lin kt ion l lin kt bn, nng lng ca lin kt ion c kJ tr ln.
Do cc c im trn iu kin thng cc hp cht lin kt ion l cc cht rn.
Gm v s cc ion m v dng lin kt vi nhau theo nhng trt t nht nh
V d: Cc mui, cc oxit v hydroxit kim loi
2.Lin kt cng ha tr:
- Lin kt cng ha tr phn cc: Nu < 2 => cp e lin kt lch v pha nguyn t
ca nguyn t c ln hn.
VD : HCl, SO2..
- Lin kt cng ha tr khng phn cc: Khi = 0 -> cp e lin kt khng b lch.
VD H2.,...
III. Lin kt cng ho tr. Phng php cp electron lin kt
1. S to thnh phn t hydro t hai nguyn t H:

Nm 1927 hai nh Bc hc Heitler v London p dng c hc lng t gii bi
ton tnh nng lng lin kt trong phn t H2. Kt qu cho thy:
- Lin kt gia hai nguyn t H c hnh thnh khi 2 electron ca hai nguyn t c
spin ngc du
- Khi hnh thnh lin kt, mt my electron khu vc khng gian gia hai ht
nhn tng ln. Do in tch m ca my electron s c tc dng ht hai ht nhn v
lin kt chng li vi nhau.
- Nu hai electron c spin cng du th mt my electron khu vc gia hai

ht nhn gim xung, mt electron khu vc ngoi hai ht nhn tng ln v cc my
ny c tc dng y nhau lm hai ht nhn tch xa nhau.=> khng hnh thnh lin kt.
Nh vy, phn t H2 c hnh thnh l do s ghp i ca 2e c spin ngc chiu

nhau. Sau , ngi ta khi qut ho cc kt qu trn v m rng thnh phng php
cp e lin kt p dng cho mi phn t.
2. Ni dung c bn ca phng php cp e lin kt
Mi lin kt cng ho tr c hnh thnh l do s ghp i ca 2e c thn c

spin ngc du ca 2 nguyn t tham gia lin kt. Khi xy ra s xen ph
gia hai my electron lin kt
Khi hai my electron xen ph nhau cng mnh th lin kt cng bn ( xen
ph cng mnh khi cc my electron tham gia xen ph c nng lng cng xp
x nhau)
Lin kt cng ho tr l lin kt c hng. Hng ca lin kt ny l hng c
xen ph cc my electron ca 2 nguyn t tham gia lin kt l ln nht
V d: S xen ph cc my s v s, s v p, p v p
s-s
s-p
p-p
3.Ho tr ca nguyn t theo phng php cp electron lin kt
T tin 1 ca phng php cp electron lin kt ta thy rng: Ho tr c th c ca
mt nguyn t c tnh bng s e c thn. Da vo iu ny ta c th gii thch c
ho tr 1 ca nguyn t H, ho tr 3 ca nguyn t N, ho tr 2,4 ca C.
V d 1: H c 1e: 1s1 H c 1e c thn nn c ho tr 1
N: 1s22s22p3
2
N c 3e c thn nn c ho tr 3
C: 1s 2s 2p
C c 2e c thn nn c ho tr 2
trng thi c bn C c 2e c thn nn c ho tr 2 (v d phn t CF2), tuy nhin C
cn c ho tr 4 (trong phn t CH4, CCl4). iu ny c gii thch nh sau: Khi c
cung cp nng lng th 1e ghp i phn lp 2s s chuyn sang trng ca phn
lp 2p, lm cho s e c thn ca nguyn t C tng ln, trng thi ny ca nguyn t C
c gi l trng thi kch thch. Trng thi kch thch l trng thi ca nguyn t c
c khi nhn thm nng lng, khi xy ra hin tng tch cc cp e chuyn 1e
sang obitan cn trng thuc cng mt lp. Nng lng tiu tn chuyn nguyn t t
trng thi c bn sang trng thi kch thch c b bng nng lng gii phng khi hnh
thnh mi lin kt ho hc.
C*:
trng thi kch thch s e c thn ca C l 4 v do c ho tr 4
V d 2: Xc nh cc ho tr c th c ca P bng phng php cp e lin kt
P (Z=15): 1s22s22p63s23p3
...
Trng thi c bn c 3e c thn c ho
tr 3
Khi c cung cp thm nng lng th 1e c ghp i ocbitan 3s s chuyn sang
1 obitan trng 3d, lm s e c thn ca nguyn t P l 5, trng thi ny ca nguyn t
P l trng thi kch thch.
Trng thi kch thch c 5e c thn c ho tr 5
Xc nh cc trng thi cng ho tr c th c ca S
S (Z=16): 1s22s22p63s23p4
Trng thi c bn c 2e c thn c ho
tr 2
3s
3p
3d
Trng thi kch thch * c 4e c thn c ho tr 4
**
Trng thi kch thch ** c 6e c thn c ho tr 6

Ch :
S dch chuyn electron i hi tiu tn nng lng, nn s dch chuyn ch
xy ra trong cng mt lp, t phn lp ny sang phn lp khc (ns np, nd,
np nd). Nng lng tiu tn c n b bng nng lng to lin kt. S
dch chuyn electron t lp ny sang lp khc khng th xy ra c, v tiu
tn nng lng qu ln khng th n b bng nng lng gii phng khi hnh
thnh lin kt
Cc nguyn t phn nhm chnh, c bit vi nguyn t chu k II, lp ngoi
cng (n=2) c 4 obitan nn cc nguyn t ny ch c ho tr ln nht l 4. Cc
nguyn t thuc chu k III c 3 phn lp ngoi cng l s, p, d nn cc nguyn
t ny c th c ho tr > 4 (P c ho tr 3, 5; S c ho tr 2, 4, 6; Cl c ho tr
1, 3, 5, 7)
Phng php tm ho tr ca nguyn t bng phng php cp e lin kt ch

ng i vi cc nguyn t nhm A (tr cc kh him).
T cc v d trn ta thy rng s lin kt cng ho tr ca 1 nguyn t l c hn,
ngha l c tnh bo ho (iu ny khc vi trng hp lin kt ion).
4. Tnh nh hng ca lin kt cng ho tr
Cc nguyn t trong phn t lin kt vi nhau theo hng c s xen ph cc my
electron l ln nht, chnh l tnh nh hng ca lin kt cng ho tr. T tnh nh
hng ny ta c th d on c cu hnh hnh hc ca phn t.
V d: Phn t H2S
H: 1s1
S: 1s22s22p63s23p4
Hai e c thn 3p ca S s to lin kt vi 2e c thn ca hai nguyn t H, s
xen ph l cc i th cc AO phi nh hng theo trc lin kt nh nhau. Do hnh
dng cc my xen ph s quyt nh cu hnh hnh hc ca phn t, do gc HSH =
90o, nhng v yu t khc nh lc y tnh in (s phn cc ca S, H) xut hin nn
thc t gc HSH l 92o2, gii thch tng t gc HSeH = 91o, HTeH = 90o.
1s
H
3py
1s
H
3pz
5. Lin kt cho - nhn

Lin kt cho - nhn cng l lin kt cng ho tr. Lin kt cho - nhn c hnh thnh
do mt cp e khng phn chia ca mt nguyn t vi 1 AO ho tr trng ca 1 nguyn t
khc. Cp e dng chung to lin kt ch do mt nguyn t (ion) cung cp.
V d:
N: 1s22s22p3
3e c thn ca N s ghp i vi 3e c thn ca 3 nguyn t H to thnh 3 lin kt
N-H. Nh vy, trong phn t NH3 cn 1 cp e cha phn chia
H
H
N:
H+: 1so c AO ho tr trng
1s
Khi NH3 tin gn ti H+ n s b ri vo trng tc dng ca H+, H+ s ht cp e cha

phn chia ca N to thnh mt lin kt N-H th t c to ra bi mt cp e cha chia
ca N v 1AO ho tr trng ca H+. Lin kt ny l lin kt cho - nhn, c k hiu
bng mt mi tn () di t nguyn t cho cp e n nguyn t nhn cp e.
H
H
S hnh thnh phn t BF4-, H3O+ u c gii thch tng t, 1 lin kt B-F v 1
lin kt H-O c hnh thnh do s cho- nhn.
Bng thc nghim ngi ta xc nhn c rng 4 lin kt N-H trong phn t NH4+
hoc phn t BF4- ging ht nhau nn lin kt cho- nhn l lin kt cng ho tr.
6. Cng ho tr cc i
Lin kt cng ho tr c to thnh do:
- Cc e c thn cha ghp i
- Mt cp e cha phn chia
- lng t trng
S lin kt cng ho tr m nguyn t c kh nng to thnh (cn gi l cng ho tr
cc i) bng s lng t ca nguyn t c kh nng tham gia lin kt (= s AO ho
tr) (bao gm lng t c 1e c thn, 1 cp e khng phn chia hay lng t trng).
V d 1:
Cc nguyn t chu k II c 4 lng t ho tr c kh nng tham gia lin kt l 2s,
2px, 2py, 2pz nn cng ho tr cc i ca chng l 4.
V d 2: B (Z=5): 1s22s22p1
B:
B*:
1s
2s
2p
B trng thi kch thch c 3e c thn, s to c ba lin kt B-F, hnh thnh phn
t BF3
F
F
B
F
Ngoi ra, nguyn t B cn 1 obitan trng, s to c lin kt B-F th t l lin kt

cho - nhn, hnh thnh phn t BF4-: C cng ho tr cc i l 4
C (Z = 6): 1s22s22p2:
C*:
C 4e c thn, nn to c 4
lin kt C-H
2 2
3
C 3e c thn to c 3 lin
N (Z= 7): 1s 2s 2p
kt N-H, hnh thnh c phn t NH3, tuy nhin trong nguyn t N cn 1 cp e cha
phn chia, c th to thnh phn t NH4+: N c cng ho tr cc i l 4
IV. Thuyt lai ha
1.iu kin ra i ca thuyt lai ha

Thuyt lai ho ra i nhm gii quyt c hai kh khn ca phng php cp electron
lin kt. Cho php gii thch c cu trc hnh hc v bn ca lin kt
VD Xt s hnh thnh CH4
C(Z=6) 1s22s22p2
trng thi kch thch C*
theo phng php cp e lin kt th 4e c thn ca C* s to thnh 4 lin kt C-H, trong
c:
- 3 lin kt p-s: 3AO 2p ca C xen ph vi 3 AO 1s ca 3 nguyn t H to 3 gc
lin kt HCH =900.
- 1 lin kt C-H th 4 to thnh do s xen ph cc AO ha tr ca 2s ca C v 1s ca H
(s-s) khng c hng xc nh trong khng gian (v mc xen ph cc AO s vi
nhau l nh nhau theo mi hng). Nu coi lin kt ny phi cch u 3 lin kt kia
th gc lin kt HCH th t phi bng 125014.. Kt qu ny cn dn n bn ca
1 lin kt C-H ( do xen ph s-s) ny khc vi bn ca 3 lin kt C-H cn li (do
xen ph p-s). (phng php cp e khng gii thch c s khc nhau ny)
- Tuy nhin thc nghim chng t rng 4 gc lin kt HCH u bng 109028 (bng
gc t din u) v bn ca 4 lin kt C-H u bng nhau.
- Gii gii quyt 2 kh khn ny ca phng php cp e lin kt-> phi dng thuyt
lai ha: gi thit rng khi to lin kt th 1 AO 2s v 3AO 2p ca C lai ha (trn ln)
vi nhau to thnh 4AO lai ha sp3 ging ht nhau hng ti 4 nh ca hnh t din
u, chng xen ph vi 4AO 1s ca 4 nguyn t H. Vy 4 lin kt C-H fi
ging nhau v cn phi bng gc ca hnh t din u m nguyn t C nm tm
ca hnh ny.
Cu hnh phn t CH4 theo thuyt lai ha

2. Ni dung thuyt lai ha:
Lai ha AO l s t hp cc AO ha tr ca 1 nguyn t to thnh 1 s tng ng
cc AO mi c cng nng lng nh hng xc nh trong khng gian v c dng
to lin kt bn hn. Cc AO tham gia t hp c th c 1e, 2e hoc l 1 lng t trng.
3. Cc kiu lai ha
a.Lai ha sp
1AOs + 1AOp 2AO lai ho sp. 2AO lai ho ny nh hng thng hng vi nhau
v to vi nhau mt gc bng 180o
V d: Dng lai ho ny gp trong nguyn t Be ca phn t BeF2, BeH2, BeCl2, nn cc

phn t ny c dng thng.
b. Lai ho kiu sp2:
1AOs + 2AOp 3AO lai ho sp2. 3AO lai ho ny nm trong cng mt mt phng
v to vi nhau gc bng 120o
+
+
120o
V d: Kiu lai ho ny gp trong nguyn t B ca phn t BF3, BCl3

c. Lai ho kiu sp3:
1AOs + 3AOp 4 AO lai ho sp3. 4 AO lai ho ny nh hng t tm ti 4 nh
ca t din u, gc to thnh gia cc AO lai ho l 109o28.
V d: Gp trong nguyn t O ca phn t H2O, nguyn t N ca phn t NH3 v ion

NH4+
4. iu kin lai ho bn:
Lai ho ca nguyn t l bn khi tho mn cc iu kin sau y:
? Cc AO nguyn t tham gia lai ho phi c nng lng xp x nhau. Nh vy,

trong mt chu k i t u n cui chu k th hiu cc mc nng lng Enp- Ens ln
dn ln. Do i t u n cui chu k hiu qu lai ho km dn.
V d: chu k II hiu qu lai ho ca cc AO(2s) v AO(2p) i vi cc nguyn t
u chu k nh Be, B, C rt tt. i vi nguyn t Be c lai ho sp v gc gia cc AO
lai l 180o, i vi B c lai ho sp2 v gc gia cc AO lai l 120o, i vi C c lai ho
sp3 v gc gia cc AO lai l 109o28
? Nng lng ca cc AO tham gia lai ho phi thp. Do cc AO lp th hai (2s,
2p) tham gia lai ho c hiu qu hn, cn cc AO lp th ba (3s, 3p) hiu qu lai ho
km hn, lp th t (4s, 4p) lai ho khng ng k.
V d: trong dy H2O - H2S- H2Se- H2Te hiu qu lai ho gim dn nn gc lin kt
gim dn theo dy 104o5 - 92o2- 91o - 90o
? xen ph ca cc AO lai ho vi cc AO nguyn t khc tham gia lin kt phi
ln.
5. D on kiu lai ho v cu trc hnh hc
chn kiu lai ho cho nguyn t trung tm da vo n l tng s lin kt ca
nguyn t trung tm vi s cp e ha tr khng phn chia.
Nu tng bng 2 th nguyn t trung tm c lai ho dng sp
Nu tng bng 3 th nguyn t trung tm c lai ho dng sp2
Nu tng bng 4 th nguyn t trung tm c lai ho sp3
-Khi bit c kiu lai ha ca nguyn t trung tm trong phn t-> cha xc nh
c cu hnh hnh hc ca phn t. V cu hnh hnh hc ca phn t ph thuc vo:
+ Dng lai ha ca ca nguyn t trung tm.
+ S lin kt ca nguyn t trung tm vi cc nguyn t xung quanh.
+S cp e ha tr ca nguyn t trung tm cha lin kt.
Mun bit cu hnh hnh hc ca 1 phn t=> phi bit 3 yu t trn.
C th:
n=2: -> lai ha sp: cu trc thng -> gc 1800
n=3: -> lai ha sp2: nu c 3 lin kt + 0 cp e ha tr cha lin kt tam gic
-> cu trc
nu c 2 lin kt + 1 cp e ha tr cha lin kt
gc.
n=4: -> lai ha sp3: nu c 4 lin kt + 0 cp e ha tr cha lin kt t din
-> thp tam
gic.
-> cu trc
gc.
V d:
BeH2 ; Nguyn t trung tm Be (Z=4)
n= s lin kt + s cp e ha tr cha lin kt
=2 +0 =2 => Be c lai ha sp => phn t c dng ng thng.
Tng t ta c:
CH4 - C c lai ho sp3- cu trc hnh hc l t din u
NH3 - N c lai ho sp3 - cu trc hnh hc l thp tam gic
H2O - O c dng lai ho sp3 - cu trc dng gc
6. nh gi u khuyt im ca phng php lin kt ha tr:
- Gii thch n gin, d hiu, cho php gii thch cu trc hnh hc ca
nhiu phn t
- Khng gii thch c s tn ti ca mt s ion nh: H2+, O2+, NO+,

khng gii thch c tnh thun t, nghch t ca phn t O2
- Khng c tnh nh (khng chng minh c)
V. Phng php MO-LCAO ( phng php MO - t hp tuyn tnh cc AO- Phng php
obitan phn t)
Nguyn tc: M rng hm sng cho phn t.

1.Nhng gi thit c bn ca phng php MO-LCAO
- Coi mi electron chuyn ng trong 1 trng gy ra bi cc ht nhn v tt c cc
electron cn li, c gi l trng t hp (khc vi trng ca nguyn t, trng
ny khng i xng cu).
- Trng thi ca electron c m t bi mt hm sng hay cn gi l obitan phn
t MO.
- Cc electron ca lp trong ca mi nguyn t khng thuc v ton b phn t m ch
thuc v nguyn t m thi, nn khng to thnh MO, c ngha l ch c cc
electron ho tr mi tham gia to thnh cc MO.
Bi ton a v gii phng trnh Shrodinger c dng: H = E
Trong H l ton t Hamilton, E l gi tr ring ca nng lng, - l hm sng m
t trng thi ca 1e trong phn t.
Gii phng trnh ny s tm c nng lng ca e trong phn t (E) v hm sng
tng ng. Sau xy dng gin nng lng v vit cu hnh e ca phn t:
Vic phn b e vo cc MO ging ht nh quy lut phn b cc e vo AO, tc l tun
theo nguyn l vng bn, nguyn l loi tr Pauli v quy tc Hund.
2. Ni dung c bn ca s to thnh MO bng phng php LCAO( Phng php
t hp tuyn tnh cc AO).
Theo phng php ny th MO c xc nh bng phng php t hp tuyn tnh
cc AO nguyn t da trn gi thuyt sau y:
Xt phn t gm hai nguyn t 1 v 2:
Khi electron chuyn ng gn nguyn t 1 th n chu tc dng ch yu ca
nguyn t 1, do obitan phn t c dng tng t nh AO ca nguyn t 1 l
1 nhng chu s nhiu lon gy ra bi nguyn t 2 nn phi c mt h s b
sung vo biu thc xc nh MO
Khi electron chuyn ng gn nguyn t 2 th n chu tc dng ch yu ca
nguyn t 2, do obitan phn t c dng tng t nh AO ca nguyn t 2 l
2 ng thi chu s nhiu lon gy ra bi nguyn t 1
T y thy rng hm tt nht m t trng thi ca electron trong phn t
s l t hp tuyn tnh ca cc AO: = C1. 1 + C2. 2
a = C1. 1 + C2. 2 vo phng trnh Schrodinger, gii ra ta s tm c
v nng lng E tng ng
V d: Xt trng hp n gin nht l ion H2+. H gm hai ht nhn ging ht nhau
AO ho tr ca nguyn t 1 l 1s c c trng bi hm sng 1, AO ho tr ca
nguyn t 2 l 1s c c trng bi hm sng 2. Khi = C1. 1 + C2. 2 l hm
m t trng thi ca electron trong phn t H2+. Thay biu thc vo phng trnh
Schrodinger, gii phng trnh s xc nh c biu thc ca MO
- MO th nht l + =
1
2
(1 + 2 ) vi nng lng tng ng l E+, nng lng
ny thp hn nng lng ca cc AO

-
MO th hai l =
1
2
(1 2 ) vi nng lng tng ng l E-, nng lng ny
cao hn nng lng ca cc AO.

+ l MO lin kt s; - l MO phn lin kt MO*, s*
S t hp ca cc AO thnh MO thng c biu din di dng gin nng
lng
s*
Eb
1s
1s a
E+
AOH
MO
AOH
H2+ ch c 1e duy nht c in vo s. iu c ngha l khi to thnh ion H2+

nng lng gim xung mt gi tr l a, ngha l h H2+ bn hn h H v H+ ring
bit.
Cu hnh electron ca H2+: s1
Tnh bc lin kt: =
NN*
2
Trong : - Bc ca lin kt hay bi ca lin kt

N - l s electron trn cc MO lin kt
N* - l s electron trn cc MO phn lin kt
=
N N * 1 0
=
= 1 / 2 0 ion H2+ c tn ti.
2
2
Gin nng lng cc MO i vi phn t H2 l: s2 => =

i vi phn t He2: s2s*2 => =
20
=1
2
22
= 0 =>phn t He2 khng tn ti.
2
Nh vy, bng phng php MO th c th gii thch c s tn ti ca ion H2+ v

nhiu phn t khc.
T phng php MO-LCAO th c nAO t hp vi nhau bng phng php t hp
tuyn tnh th thu c n MO, i vi s to thnh phn t A2 s c: n/2MO lin kt c
nng lng thp hn nng lng ca cc AO em t hp v n/2 MO phn lin kt (MO*)
c nng lng cao hn nng lng ca cc AO em t hp.
3. Cch kho st cu trc phn t theo phng php MO
* iu kin cc AO c kh nng t hp vi nhau l:

- Cc AO tham gia t hp vi nhau phi c nng lng xp x nhau
- Cc AO tham gia t hp phi xen ph nhau r rt cho nn ch cn xt s t hp
ca cc AO ho tr lp ngoi cng
- Cc AO tham gia t hp ca hai nguyn t phi c tnh i xng ging nhau
i vi trc lin kt
* Phn loi cc MO:
Da vo tnh i xng ca cc MO hay tnh i xng ca phn xen ph gia cc AO
ho tr, phn loi cc MO nh sau:
- MO: c to ra khi phn xen ph ca cc AO c tnh i xng trc
ns(1) + ns(2) s v s*
npz(1) + npz(2)
z v z*
npz(1) + ns(2) v *
ns(1) + npz(2) v *
- MO: c to ra nu phn xen ph ni trn c mt ct cha trc ni hai ht nhn
npx(1) + npx(2) x v x*
npy(1) + npy(2) y v y*
* V gin nng lng ca cc MO:
- Cc AO t hp c nng lng cng thp th mc nng lng ca cc MO thu
c cng thp
- Khi hai AO tham gia t hp xen ph nhau cng mnh th s tch cc mc nng
lng cng ln, ngha l s chnh lch gia MO lin kt v MO phn lin kt cng ln
* Tnh s electron ho tr ca phn t v xp cc electron vo cc MO theo quy
tc sau y:
- Nguyn l Pauly: Mi MO xp ti a 2e
- Nguyn l vng bn: Cc electron c xp ln lt vo cc MO c nng
lng t thp n cao
- Quy tc Hund: Nu c nMO c mc nng lng bng nhau th cc electron c
khuynh hng chim u vo cc MO sao cho s electron c thn l ln nht
* Xc nh cc c trng c bn ca phn t
- Tnh bc lin kt:
=
NN*
2
Trong : - Bc ca lin kt hay bi ca lin kt
N - l s electron trn cc MO lin kt

N* - l s electron trn cc MO phn lin kt
T bc lin kt suy ra bn ca lin kt v di lin kt. cng ln th lin kt
cng bn v di lin kt cng ngn v ngc li. = 0 th khng to lin kt.
- Xc nh t tnh ca phn t:
Khi trong phn t c electron c thn th phn t b t trng ngoi ht v cht
c gi l cht thun t. Khi s electron c thn cng ln th tnh thun t cng
mnh.
Nu trong phn t khng c electron c thn th cht b t trng ngoi y v
cht c gi l cht nghch t.
4. Kho st mt s phn t A2 theo phng php MO (A thuc chu k II)
a. Tm cc MO
Nguyn t A c 4AO ho tr l 2s, 2px, 2py, 2pz, cc phn lp trong s khng tham
gia t hp
Cc AO c tnh i xng ging nhau s t hp li vi nhau v to nn cc MO tng
ng nh sau:
AO(2s) + AO(2s) MOs v MOs*
2px + 2px
x v x*
2py + 2py
y v y*
2pz + 2pz
z v z*
b. V gin nng lng cc MO
Ngoi ra, c th vit di dng dy th t cc mc nng lng t thp n cao nh

sau:
(KK) s s*z x=y x*=y*z* (dy 1). Bng thc nghim chng t rng dy 1 ch
ng i vi cc nguyn t cui chu k: O2 F2 Ne2
Cn i vi cc nguyn t u chu k t Li2 n N2 tun theo dy 2:
(KK) s s* x=y z x*=y*z* (dy 2). iu ny c gii thch do s y nhau
gia cc mc nng lng s* v z, v i vi cc nguyn t u chu k mc nng
lng cc AO2s v AO2p xp x nhau.
c. Sp xp cc electron ho tr ca phn t vo cc MO theo nhng nguyn l thch
hp
Phn t
Li2 (Z=3)
Be2 (Z=4)
B2(Z=5)
C2(Z=6)
N2(Z=7)
O2(Z=8)
F2(Z=9)
S electron ho
tr
2
4
6
8
10
12
14
Cu hnh electron
(KK) s2
(KK) s2s*2
(KK) s2s*2 x1=y1
(KK) s2s*2 x2=y2
(KK) s2s*2 x2=y2 z2
(KK) s2s*2 z2 x2=y2 x*1=y*1
(KK) s2s*2 z2 x2=y2 x*2=y*2
1
0
1
2
3
2
1
5. Cc phn t khng i xng AB (B >A)

* Nguyn tc:
Phn t c cu to bi hai nguyn t khc nhau, v d: CO, NO, CN-
Cng chn cc AO tham gia t hp to thnh cc MO phn t theo nguyn tc trn,
nhng ch n mc nng lng ca cc AO. Cc AO tham gia t hp phi c mc
nng lng xp x nhau.
Nu gia hai nguyn t A v B m m in ca B ln hn m in ca A th
mc nng lng AO ca B thp hn mc nng lng AO tng ng ca A nn MO lin
kt thu c s nm gn mc nng lng AO ca B, cn MO phn lin kt thu c s
nm gn mc nng lng AO ca A. Ni chung phn t AB chu k 2 c dy nng lng
cc MO tng t cc phn t A2 u chu k 2.
V d 1: Vit cu hnh electron ca phn t CO
2s(C) + 2s(O) s v s*
2px(C) + 2px(O) x v x*
2py(C) + 2py(O) y v y*
2pz(C) + 2pz(O) z v z*
Tng electron ho tr l 10: (KK) s2s*2 x2=y2 z2
Tng t kho st cc phn t CN, CN-, NO v NO+
82
=3
2
V d 2: Phn t HF
Tham gia t hp to MO gm AO(1s) ca H v 2pz ca F to thnh MO v MO*
do tnh i xng ging nhau. Ngoi ra, nguyn t F cn c 2 obitan ho tr 2px v 2py
khng c obitan tng ng ca nguyn t H cng t hp. Cc AO ny vn nh ch
ti nguyn t F v c mc nng lng nh trong nguyn t, trong phn t chng c
gi l cc MO khng lin kt.
2px 2py 2pz
Cu hnh e: HF s2nx2=ny2
20
=1
2
Ghi ch:
- Kt qu thu c ph hp vi phng php cp electron lin kt
- Tuy nhin c u im hn so vi phng php cp electron lin kt l c th
gii thch c s tn ti ca lin kt c bi l thp phn v d nh F2+, H2+, O2+, O2
- Gii thch c tnh thun t v nghch t ca nhiu phn t
B- Cu to phn t
I. phn cc ca phn t:
1. Phn t c cc v khng cc
Phn t khng phn cc l phn t c cu to hon ton i xng nn trng tm ca
in tch (+) v trng tm ca in tch (-) ca phn t trng ln nhau
V d: Phn t gm hai nguyn t ging nhau nh H2, O2, N2, hoc phn t c cu
to i xng nh CH4, BF3, BF4-
Phn t c cc l phn t c cu to khng i xng, do trng tm ca in tch
(+) v trng tm in tch (-) khng trng nhau
V d: Phn t HCl, HF, H2O, NH3
2.M men lng cc ca phn t ()
Mi phn t c cc l mt lng cc in gm hai in tch ngc du (+q) v (-q)
t cch nhau mt khong l l
q
-
nh gi phn cc ca phn t ngi ta a ra mt i lng l momen lng

cc = q.l (C.m) hay (D : debye), 1D = 3,33.10-30 Cm
Trong : q l gi tr tuyt i ca in tch , C (Coulomb)
l l di lng cc, m
Momen lng cc l mt i lng c hng. Ngi ta quy c chiu hng t
trng tm ca in tch (+) n trng tm ca in tch (-).
Momen lng cc c trng cho phn cc ca phn t: cng ln th phn t
cng phn cc: cc phn t cng ho tr c trong khong t 0 n 4D, cc phn t ion
c trong khong t 4 - 11D.
Mmen lng cc ph thuc vo nhiu yu t nh: s chnh lch m in gia cc
nguyn t tham gia lin kt, tnh i xng ca phn t, cc cp electron t do
V d:
+ Phn t HCl c = 1,04D, phn t HI c = 0,44D
+ Phn t CO2 c cu trc thng:
O
phn cc do =0.
c tng=0, cc lin kt C=O phn cc mnh nhng phn t CO2 khng
V d: Hai phn t NH3 v NF3 u c cu to l thp tam gic, ng l phn cc

ca hai phn t ny phi bng nhau nhng thc t NH3 = 1,46D v NF3 = 0,2D, iu ny
c gii thch nh sau:
4
3
2
H
1
F
NH3 = 1 + 2 + 3 + 4
N
2
NF3 = 1 + 2 + 3 4
Trong phn t NH3 momen lng cc ca cp electron t do cng chiu vi momen

lng cc ca cc mi lin kt N-H do tng momen lng cc ca phn t l ln.
Cn trong phn t NF3 hng ca cp electron t do ngc chiu vi ca cc mi
lin kt N-F do tng ca phn t NF3 nh hn.
3. S phn cc ho phn t
Di tc dng ca in trng ngoi cc phn t b bin dng v thay i cu trc, do
momen lng cc phn t b thay i. l hin tng phn cc ho phn t.
* Hin tng phn cc ho phn t
Di tc dng ca in trng ngoi gy ra bi hai t in, cc phn t c cc c
sp xp li theo phng ca in trng, l s phn cc nh hng
+
-
+
+
+
+
+
+
+
+
+
-
+
-
+ + -
Mt khc, mi momen lng cc cng b ko di ra lm tng tr s ca momen lng

cc phn t, l s phn cc bin dng.
i vi cc phn t khng cc: Khi t trong in trng gia hai bn t in th cc
my electron b ht v bn (+) ca t in, cn ht nhn b ht v pha bn (-), kt qu
trong phn t xut hin mt momen lng cc cm ng, y l hin tng phn cc ho
cm ng.
Cc mi lin kt yu:
Ngoi cc mi lin kt ho hc nh lin kt cng ho tr, lin kt ion c nng lng
c vi trm kJ/mol tr ln, cn gp nhiu loi lin kt yu hn c nng lng c vi chc
kJ/mol l lin kt hydro v lc Van der Waals. Cc lin kt yu ny c vai tr quan
trng trong qu trnh chuyn trng thi nh bay hi, nng chy, chuyn dng th hnh
1. Lin kt hydro:
L lin kt ph, nguyn t H sau khi lin kt vi nguyn t X c m in ln li c
kh nng lin kt ph vi mt nguyn t khc cng c m in ln
* C ch to lin kt hydro: nguyn t H khi lin kt vi nguyn t X c m in
ln nh F, O, N th cp electron ho tr s b lch v pha nguyn t X, nguyn t H ch
cn li ht nhn tch in dng, do n c kh nng lin kt vi nguyn t khc cng
c m in ln v lin kt ny c gi l lin kt hydro.
V d: H + F ... H + F
* Nng lng ca lin kt H c 8- 40 kJ.mol-1. Nng lng ca lin kt hydro cng
ln khi m in ca nguyn t lin kt vi n cng ln v kch thc cng nh
* nh hng ca lin kt hydro:
Nng lng ca lin kt hydro nh so vi cc lin kt khc nn hu nh n ch nh
hng n tch cht l hc ca cc cht nh nhit si, nhit nng chy hay kh
nng ho tan gia cc cht.
V d:
- Do lin kt hydro gy ra hin tng lin hp phn t: (HF)n: n= 2-4; (H2O)n:
n= 2-3. Do hin tng lin hp phn t lm cho cc cht tr nn kh bay hi, do lm
tng nhit si, nhit bay hi. HF c nhit si, nhit bay hi cao hn nhiu so
vi HCl, HBr, HI. H2O c nhit si v nhit bay hi cao hn nhiu so vi H2S,
H2Se, H2Te.
- Do lin kt H lm gim kh nng in ly ca nhiu cht: HF l axit yu, cht
in ly yu trong HCl, HBr, HI l axit mnh
- Gy ra s bt thng v t khi ca nc: thng thng khi nhit tng th t
khi ca cc cht gim xung, nhng i vi nc t < 4oC th t khi ca nc tng
theo nhit v t gi tr cc i 4oC v sau t khi li gim dn theo nhit .
2. Lc gia cc phn t:
Thc nghim cho thy, gia cc phn t ca mt cht (k c cc phn t khng phn
cc) lun tn ti lc tng tc, gi l lc Van der Waals. Lc Vander Waals gi vai tr
quan trng trong qu trnh chuyn trng thi tp hp.
Bn cht ca lc Van der Waals gm c ba loi lc sau:
* Lc nh hng:
Tn ti trong cc phn t phn cc. Cc phn t phn cc ht ln nhau bng cc in

tch ngc du ca lng cc phn t, do cc phn t ny nh hng vi nhau theo
mt hng xc nh. cng ln th lc nh hng cng ln.
* Lc cm ng:
Xut hin gia cc phn t c cc v khng cc. Khi phn t khng cc tin gn n
phn t c cc th di tc dng ca in trng gy ra bi phn t phn cc th cc
phn t khng cc b cm ng in v to thnh lng cc cm ng
* Lc khuch tn:
Do s chuyn ng khng ngng ca electron v chuyn ng dao ng ca ht nhn
gy nn s bt i xng tm thi v s phn b trng tm in tch (+) v in tch (-) to
nn momen lng cc tm thi trong phn t. Lng cc tm thi lun xut hin, trit
tiu, i du.S xut hin lng cc ny v s mt i xy ra mt cch nhp nhng to
thnh mt lc ht thng xuyn gi l lc khuch tn.
* c im ca lc Van der Waals
Khng c tnh chn v bo ho
Nng lng nh hn 40 kJ/mol-1
Lc Van der waals cng ln khi phn t c momen lng cc ln, c kch thc v
khi lng ln.
Ti liu tham kho:

1. Nguyn nh Chi, C S L Thuyt Ha Hc, NXB GD, 2004.
2. Nguyn Hnh, , C S L Thuyt Ha Hc, Tp 2, NXB GD 1997.
3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT,
2000.
Bi ging mn C s l thuyt Ha hc
PHN I: NHIT NG HO HC
Mun xt mt phn ng ho hc c thc hin c hay khng cn bit:
- iu kin no th phn ng xy ra v xy ra n mc no?
- Phn ng xy ra nh th no? Nhanh hay chm? Nhng yu t no nh hng
n tc phn ng?
Khi tr li c c hai cu hi ny, ngi ta c th iu khin c phn ng,
tm c iu kin ti u thc hin phn ng, nhm t hiu qu cao nht.
Cu hi th nht l i tng ca nhit ng ho hc, cn cu hi th hai l i
tng ca ca ng ho hc.
Nhit ng hc l b phn ca vt l hc, nghin cu cc hin tng c v nhit,
cn nhit ng ho hc l b phn ca nhit ng hc nghin cu nhng quan h nng
lng trong cc qu trnh ho hc.
CHNG I: P DNG NGUYN L TH NHT

CA NHIT NG HC VO HO HC
I. MT S KHI NIM M U
1. Kh l tng:
-
Cht kh c coi l l tng khi m khong cch gia cc phn t kh xa nhau,

c th b qua s tng tc gia chng v coi th tch ring ca cc phn t kh l
khng ng k (kh c p sut thp).
Phng trnh trng thi ca kh l tng: nu c n mol kh p sut P, nhit T

v chim th tch V th: PV = nRT =
m
RT
M
(1.1)
trong : m- khi lng ca kh, g

M: Khi lng mol ca kh, g
T Nhit tuyt i, K ( T = t0C +273)
R: Hng s kh l tng, ty theo n v ca P v V m c ga tr
khc nhau:
- Nu P (atm), V(dm3=l) R = 0,082 atm.l.K-1.mol1
- Nu P (Pa=N/m2), V(m3) R = 8,314 J.K-1.mol-1
1atm = 1,013. 105 Pa= 1,013. 105N/m2= 760 mmHg
- Nu trong bnh c mt hn hp kh th mi kh gy nn mt p sut gi l p sut ring
phn ca kh v c k hiu l Pi .Tng tt c cc p sut ring phn bng p sut
chung P ca hn hp.Nu gi V l th tch chung ca hn hp kh ( bng dung tch bnh
ng th phng trnh kh kh l tng c dng:
P = Pi =
ni RT
V
n i
(1.2)
: Tng s mol kh trong hn hp.
p sut ring phn Pi ca kh i trong hn hp c th tnh:

Pi = ni
n
RT
hoc Pi= NiP vi Ni = i
n i
V
(1.3)
2. H v mi trng
- H: H l i tng cn nghin cu cc tnh cht nhit ng hc. i km vi khi nim
h l khi nim mi trng xung quanh, l ton b phn cn li ca v tr bao quanh h.
H c phn cch vi mi trng xung quanh bng mt mt thc hay tng tng.
- C 4 loi h:
+ H c lp: l h khng trao i cht v nng lng vi mi trng
+ H m: l h trao i cht v nng lng vi mi trng.
+ H kn l h ch trao i nng lng vi mi trng

+ H khng trao i nhit vi mi trng c gi l h on nhit.
3.Quy c v du trong qu trnh trao i nng lng
Nng lng trao i gia h v mi trng c th l cng , nhit, nng lng in...
-
H nhn nng lng: du (+)
H nhng nng lng du ()
4.Trng thi ca h v cc thng s trng thi:

- Trng thi v m ca mt h c c trng bng nhng i lng xc nh nh: t0C, P,
V, C...Cc thng s ny c th o c, gi l cc thng s trng thi.
v d: gia s mol kh n, nhit T v p sut P ca mt h kh (gi s l kh l tng)
c mi quan h cht ch, c biu din bng phng trnh trng thi ca kh l tng
PV=nRT.
- C hai loi thng s trng thi: dung v cng
+ Thng s trng thi dung l nhng thng s trng thi t l vi lng cht, th d
th tch, khi lng.
+ Thng s trng thi cng khng t l vi lng cht, v d nhit p sut, nng
, nht.
5. Trng thi cn bng ca h
L trng thi ti cc thng s trng thi ca h khng i theo thi gian. VD phn ng
thun nghch CH3COOH + C2H5OH <=> CH3COOC2H5 + H2O t trng thi cn bng
khi nng ca 4 cht khng bin i .
6. Bin i thun nghch v bin i bt thun nghch
- Nu h chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc v
cng chm qua lin tip cc trng thi cn bng th s bin i c gi l thun
nghch.y l s bin i l tng khng c trong thc t.
- Khc vi s bin i thun nghch l s bin i bt thun nghch. l nhng bin i
c tin hnh vi vn tc ng k. Nhng bin i xy ra trong thc t u l bt thun
nghch.
7.Hm trng thi
- Mt hm F( P,V,T...) c gi l hm trng thi nu gi tr ca n ch ph thuc vo
cc thng s trng thi ca h m khng ph thuc vo cch bin i ca h.
- V d: n mol kh l tng:
+ trng thi 1 c c trng bng P1V1=nRT1
+ trng thi 1 c c trng bng P2V2=nRT2
PV l mt hm trng thi, n khng ph thuc vo cch bin i t trng thi 1
sang trng thi 2.
8.Cng v nhit: L hai hnh thc trao i nng lng.

Cng W (J, kJ)
Nhit Q (J, kJ)
Cng v nhit ni chung khng phi l nhng hm trng thi v gi tr ca chng ph
thuc vo cch bin i.
* Cng gin n ( cng chuyn dch)
W
= - Pngoi.dV =-PndV
(1.4)
W ph thuc vo Pn ( v h sinh cng nn c du -).

2
Nu qu trnh l hu hn => W = Pn dV
1
(1.5)
Nu gin n trong chn khng Pn =0 W=0.

Nu gin n bt thun nghch: gin n chng li Pn khng i:
Pn= const (Pn=Pkq) Wbtn = -Pn(V2-V1)
(1.6)
Nu gin n thun nghch: tc l Pn =Ph

V2
Wtn= Pn dV
(1.7)
V1
Nu kh l l tng v gin n ng nhit c :

Pn = Ph =
V2
V
nRT
dV
=> WTN = nRT
= nRT ln 2
V
1
V
V1
V
Vy WTN =- nRT ln
V2
P
=- nRT ln 1
V1
P2
(1.8)
II. NGUYN L I P DNG VO HA HC

1. Khi nim ni nng (U)
Nng lng ca h gm 3 phn
-
ng nng chuyn ng ca ton h
Th nng ca h do h nm trong trng ngoi
Ni nng ca h
Trong nhit ng ho hc nghin cu ch yu ni nng.

Ni nng ca h gm:
-
ng nng chuyn ng ca cc phn t, nguyn t, ht nhn v electron (tinh

tin, quay..)
Th nng tng tc (ht v y) ca cc phn t, nguyn t, ht nhn v electron.
Nh th ni nng (U) ca h l mt i lng dung , gi tr ca n ch ph thuc

vo trng thi vt l m khng ph thuc vo cch chuyn cht ti trng thi . N l
mt hm trng thi.
Ni nng ca h ph thuc vo bn cht, lng ca n, p sut. nhit ,th tch v

thnh phn.
i vi kh l tng ni nng ca h ch ph thuc vo nhit .
2. Pht biu nguyn l I ca nhit ng hc
Nguyn l I ca nhit ng hc v thc cht l nh lut bo ton nng lng:
Nng lng ca mt h c lp lun lun bo ton.
a.Tn ti mt hm trng thi U gi l ni nng. dU l mt vi phn ton phn.
b. S bin i ni nng U ca h kn chuyn t trng thi 1 sang trng thi 2 bng tng
i s ca tt c cc nng lng trao i vi mi trng trong qu trnh bin i ny (d
l bin i thun nghch hay bt thun nghch).
U
= U2-U1 = WA + QA =WB + QB =...=const
trong W l Q l cng v nhit lng m h trao i vi mi trng.

i vi mt bin i v cng nh
dU= W + Q
dU: vi phn ton phn
W v Q : khng phi l vi phn ton phn.
i vi mt bin i hu hn
2
U = dU = W + Q
(1.9)
Nu: + Trng thi u v cui nh nhau U = dU = 0 --> W+Q=0

+ H c lp: W = Q = 0 --> U =0
3. Nhit ng tch, nhit ng p
a.Nhit ng tch.( V = const)
Xt 1 h kn, c T, V = const, h ch sinh cng c hc:
W = pdV v V = const W = pdV = 0
Theo nguyn l I: dU= W + Q

Do : dU= Q v U =
Q = Q
(1.10)
v = const
Qv l nhit ng tch, gi tr ca n ch ph thuc vo trng thi u v cui ca h.

b. Nhit ng p(P= const)
Xt h kn, thc hin c T, P =const, h ch sinh cng c hc:
2
W= pdV = P(V 2 V1 )
1
= U2-U1 = W + Q
U2 - U1 = Qp-P(V2-V1) hay Qp = (U2+PV2) (U1+PV1)

QP: Gi l nhit ng p
H=U+PV
Ta c: Qp= H2-H1 = H
(1.11)
H c gi l entapi, n l hm trng thi v U v PV u l nhng hm trng thi.

III. NHIT PHN NG HO HC.
1. Nhit phn ng
L nhit lng thot ra hay thu vo khi phn ng xy ra theo ng h s t lng,
cht tham gia v sn phm cng mt nhit T.
c th so snh nhit ca cc phn ng cn ch r iu kin phn ng xy ra:
-
Lng cc cht tham gia v sn phm to thnh theo h s t lng.
Trng thi vt l ca cc cht
Vi mc ch ny ngi ta a ra khi nim trng thi chun. Trng thi chun ca

mt cht nguyn cht l trng thi l hc di p sut 101,325kPa(1atm) v nhit
kho st n bn nht.
V d: Cacbon tn ti hai dng th hnh l graphit v kim cng. 298K v di p
sut 101,325kPa, graphit l bin i th hnh bn nht do trng thi chun 298K ca
cacbon l graphit.
-
Nu phn ng c thc hin P=const th nhit phn ng c gi l nhit phn

ng ng p Qp= H .
Nu phn ng c c thc hin V=const th nhit phn ng c gi l

nhit phn ng ng tch Qv= U .
Phn ng ta nhit v phn ng thu nhit

-
Phn ng ta nhit: l phn ng nhng nhit lng cho mi trng. Khi

H = QP <0 hoc U = QV <0. V d phn ng ti vi
Phn ng thu nhit: l phn ng nhn nhit lng t mi trng. Khi

H = QP >0 hoc U = QV >0. V d phn ng nung vi..
Quan h gia nhit ng tch v nhit ng p:

H = (U + pV ) p = U + pV
Qp= Qv+ nRT
(1.12)
Trong : n = s mol sn phm kh s mol cht kh tham gia phn ng.

R = 8.314 J/mol.K: hng s kh l tng
T: K
V d: C6H6 (l) +
15
O2(k) = 6CO2(k) + 3H2O(l)
2
n= 6-7,5=-1,5.
C(r) + O2(k) = CO2(k)

n= 1- 1= 0
2. Nhit sinh chun ca mt cht:

L nhit ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun
(cht sn phm v cht phn ng phi l cc cht nguyn cht 1atm v gi P, T=const,
cc s liu nhit ng chun trong cc ti liu thng c xc nh nhit T=298
K).
K hiu H T0,s (kJ.mol-1)
0
Nu T =298 => H 298
,s
-1
0
0
V d: H 298
, s (CO2)=-393,51(kJmol ). N l nhit phn ng ca phn ng sau 25 C
khi pO = pCO = 1atm

2
Cgr + O2(k) = CO2(k).

C graphit l n cht bn nht ca cacbon 1 atm v 298K.
- T nh ngha trn ta suy ra nhit sinh chun ca n cht bn bng khng.
3. Nhit chy chun ca mt cht:
L nhit ca qu trnh t chy han ton 1 mol cht bng O2 to thnh cc xit bn
nht ( vi ha tr cao nht ca cc nguyn t), khi cc cht trong phn ng u nguyn
cht P=1atm v gi T, P khng i (thng T=298K).
-1
H T0,c (kJ.mol )
-1
0
ng vi nhit ca phn ng sau 250C v p=const
V d: H 298
,c (CH 4 ) =-890,34kJ.mol
khi PCH = PO = PCO = 1atm .

4
CH4 (k)+ 2O2 (k) CO2 (k) + 2H2O(l)

Tt c cc xit bn vi ha tr cao nht ca cc nguyn t u khng c nhit chy.
IV.NH LUT HESS V CC H QU
1.Pht biu: Hiu ng nhit ca mt phn ng ch ph thuc vo trng thi u v trng
thi cui ca cc cht tham gia v cc cht to thnh ch khng ph thuc vo cc giai
on trung gian, nu khng thc hin cng no khc ngoi cng gin n.
H
V d:
Cgr
H 1
O2(k)
CO2(k)
H 2
CO(k) + 1/2 O2(k)

Theo nh lut Hess:
H = H 1 + H 2
(1.13)
2.Cc h qu
H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch

nhng ngc du.: H t = H n
(1.14)
H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht cui tr i

tng nhit sinh ca cc cht u.
H = H s (s nph m ) H s (thamgia )
(1.15)
Nu iu kin chun v T=298K th

H 0 298, pu = H 0 298,s (s nphm ) H 0 298,s (thamgia )
(1.16)
T nh ngha ny suy ra: nhit sinh ca mt n cht bn vng iu kin chun

bng khng: H T0, s (n cht) = 0.
V d: Tnh H0 ca phn ng:
C2H4(k) + H2 (k) --> C2H6 298K?
-1
0
Cho bit H 298
, s ca cc cht (kJ.mol ) nh sau:
C2H4(k): +52,30
C2H6(k): -84,68
Gii:
Ta c:
0
H 298
0
0
0
= H 298
, s (C2H6(k)) - [ H 298, s (C2H4(k)) + H 298, s (H2(k))]
=-84,68-52,30-0
=-136,98kJ.mol-1
H qu 3: Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht u tr i
tng nhit chy ca cc cht cui.
H p = H c (tg ) H c (sp)
(1.17)
Nu iu kin chun v T=298K th

H 0 298, p = H 0 298,c (tg ) H 0 298,c (sp)
(1.18)
3.Cc ng dng
* nh lut Hess v cc h qu ca n c mt ng dng rt ln trong Ho hc, n cho
php tnh hiu ng nhit ca nhiu phn ng trong thc t khng th o c.
V d1: khng th o c nhit ca phn ng Cgr + 1/2 O2(k) =CO(k) v khi t chy
Cgr ngoi CO (k) ra cn to thnh CO2(k) nhng nhit ca cc phn ng sau y o
c:
0
Cgr + O2(k) = CO2(k) H 298
=-393513,57 J.mol-1
0
CO(k) + O2(k) = CO2(k) H 298
=-282989,02 J.mol-1
tnh c nhit ca phn ng trn ta hnh dung s sau:
Cgr +
O2(k)
CO2(k)
x=?
CO(k) + 1/2O2(k)
Trng thi u (Cgr+O2) v trng thi cui (CO2(k)) ca c hai cch bin i l nh nhau,
do theo nh lut Hess:
-393.513,57 =
282.989,02
x=-110507,81J.mol-1
V d 2: Xc nh nng lng mng lui tinh th ca NaCl(r) bit
+ Nhit nguyn t ha Na(r)
H1 = +108.724 J .mol 1
Na(r) Na(h)
+ Nhit phn ly Cl2(k)
H 2 = +242.672 J .mol 1
Cl2(k) 2Cl(k)
+ Nng lng ion ha Na(h)

Na(h) Na+(h) + e
H 3 = +489.528 J .mol 1
+i lc i vi electron ca Cl(k)
Cl(k) + e Cl-(k)
H 4 = 368.192 J .mol 1
+Nhit ca phn ng
Na(r) + 1/2 Cl2(k) NaCl H 5 = 414.216 J .mol 1
xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born
Haber:
Trng
thi u
Na(r) + 1/2 Cl2(k)

H1
1/2
Na(h) + Cl(k)
H5
NaCl(r)
Trng
thi cui
x=?
H3
H4
Na+(h) + Cl-(k)
Theo nh lut Hess ta c:

H 5 = H1 + 1 / 2H 2 + H 3 + H 4 + x
x= H 5 (H1 + 1 / 2H 2 + H 3 + H 4 )
x= -765.612J.mol-1
V. S PH THUC HIU NG NHIT VO NHIT .NH LUT KIRCHHOFF
1. Nhit dung mol ca 1 cht

L nhit lng cn thit nng nhit ca 1 mol cht ln 1K v trong sut qu trnh
ny khng c s bin i trng thi(nng chy, si, bin i th hnh...)
- n v thng dng ca C l: J.K-1mol-1

- Nhit dung mol ng p. Qu trnh c thc hin P=const.
dH
H
CP=
=
T p dT
dH = CP dT
=> dH=CpdT =>
==> H = C P dT
1
-Nhit dung mol ng tch. Qu trnh c thc hin V=const.

2
dU
U
Cv=
=
T v dT
U = Cv dT
=> dU=CvdT =>
==> U = C v dT
1
2.Nhit chuyn pha

-Chuyn pha: bay hi ,nng chy, ng c, thng hoa...
- H cf l nhit lng trao i vi mi trng khi 1 mol cht chuyn pha. P=const, khi
mt cht nguyn cht chuyn pha th trong sut qu trnh chuyn pha, nhit khng
thay i.
3. nh lut Kirchhoff
Xt 1 h kn, P=const.. Xt phn ng sau thc hin bng hai con ng:
H 2
n1A + n2B
n3C + n4D
T2
H b
Ha
H1
n1A + n2B
n3C + n4D
T1
Theo nh lut Hess ta c H 2 = H1 + H a + H b

T1
T2
H a = (n1C P + n 2 C P ) dT = (n1C P + n2 CP )dT

A
T2
T1
T2
Hb = (n3CPC + n4CPD )dT

T1
T2
T H2 = H1 + [(n3CP + n4CP ) (n1CP + n2CP )]dT

C
T1
T2
=> H T = H T + C P dT => Cng thc nh lut Kirchhoff

2
T1
Vi: C P = C P (sp) C P (tg )
iu kin chun(P=1atm) v T1=298 K c:

T
H = H
0
T
0
298
+ C P0 dT
298
Nu trong khong hp ca nhit => coi C P0 = const th

H T0 = H 2980 + C P0 ( T 298)
4.Mi quan h gia nng lng lin kt v nhit phn ng

C th quy uc nng lng lin kt (Elk) tng ng vi nng lng ph v lin kt hoc
hnh thnh lin kt.
y ta qui c Elk ng vi qu trnh ph v lin kt: nng lng lin kt l nng
lng ng vi qu trnh ph v lin kt do nng lng lin kt cng ln th lin kt
cng bn.
- Mt phn ng ho hc bt k v bn cht l ph v lin kt c v hnh thnh cc lin
kt mi do Hp c th c tnh qua Elk ca cc lin kt ho hc.
V d1: Ph v 1 mol thnh cc nguyn t c lp:
H2(k,cb) --> H(k,cb) + H (k,cb)
0
298K, p= 1atm => EH-H = +432kJ.mol-1 = H 298
Trong trng hp ny Elk coi nh hiu ng nhit ca qu trnh.

V d2: Xt phn ng N2(k) + 3H2(k) => NH3(k). Thc hin bng 2 con ng
N2(k) + 3H2(k)
EN-N
3EH-H
2NH3(k)
-6EN-H
2H(k) + 6H(k)
H = EN N + 3E H H 6 EN H
Ti liu tham kho:

3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT, 2000.
CHNG II: NGUYN L II CA NHIT NG HC CHIU V GII HN
T DIN BIN CA QU TRNH
M U
Trong t nhin, cc qu trnh l hc v ho hc xy ra theo chiu hon ton xc nh.
- Nhit t truyn t vt nng sang vt lnh hn
- Kh t truyn t ni c p sut cao n ni c p sut thp
- Cc phn ng ho hc t xy ra, v d: Zn + HCl --> ZnCl2 + H2
Cn cc qu trnh ngc li th khng t xy ra c.
Nguyn l I cho php tnh nhit ca cc phn ng nhng khng cho php tin
on chiu v gii hn ca qu trnh
Nguyn l II cho php gii quyt cc vn ny.
I.NGUYN L II. HM ENTROPY
1.Nguyn l II (Tiu chun xt chiu ca qu trnh)
- Tn ti mt hm trng thi gi l entropi (S).
- nhit T khng i, trong s bin i v cng nh, h trao i vi mi trng mt
nhit lng Q th bin thin entropi ca qu trnh c xc nh:
Q
Nu l bin i thun nghch: dS = TN
T
Nu l bin i bt thun nghch: dS >
QbTN
T
Tng qut
dS
Du > : qu trnh bt thun nghch
T
2
Du = : qu trnh thun nghch
* Ch :
V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc
2
l:
S BTN = S TN =
1
QTN
T
2
S TN = S BTN >
1
Qbtn
T
==> QTn> QBTN : Nhit qu trnh thun nghch ln hn nhit qu trnh bt thun nghch.
+ xc nh Sbtn , trc ht hnh dung mt qu trnh thun nghch c cng trng
thi u v trng thi cui vi qu trnh bt thun nghch, sau tnh S theo cng thc:
2
S =
1
QTN
T
(khng xc nh c trc tip Sbtn)
2. Nguyn l II p dng trong h c lp
i vi h c lp:
Qtn= 0 --> S = 0
Qbtn=0 --> S > 0
Nh vy i vi h c lp:
- Trong qu trnh thun nghch (cn bng), entropi ca h l khng i.
- Trong qu trnh bt thun nghch ngha l t xy ra, entropi ca h tng.
iu ny c ngha rng trong cc h c lp, entropy ca h tng cho ti khi t ti gi
tr cc i th h t ti trng thi cn bng.o li ta c th ni:
Trong h c lp:
- Nu dS >0 ( S tng)
h t din bin
2
- Nu dS=0, d S<0 (S max) h trng thi cn bng.
3. ngha hm entropi
a. Entropi l thc o hn n ca h
Xt 1 h c lp T=const, h gm 2 bnh c th tch bng nhau, ng 2 kh l tng
A v B c pA=pB u thp. Hai bnh c ni vi nhau bng mt dy dn c kho K.
M K--> 2 kh khuch tn vo nhau cho n khi c s phn b ng u trong ton b
th tch ca 2 bnh.
S khuch tn cc kh l tng vo nhau l qu trnh c T=const(Q=0) --> S > 0
(S2> S1) --> hn n ca trng thi cui (hn hp 2 kh) c trng bng S2 ln hn
hn n ca trng thi u ( mi kh 1 bnh ring bit) c trng bng S1.
Vy trong h c lp, qu trnh t xy ra theo chiu tng hn n ca h (tng
entropi, S > 0 ). Qu trnh ngc li: Mi kh t tch ra khi hn hp kh tr li trng
thi u khng th t xy ra.
* Kt lun:
- Entropi c trng cho hn n: hn n ca h cng ln th S cng ln.
- Nu s ht trong h cng ln--> hn n cng ln--> Sln
- Lin kt gia cc ht trong h cng yu --> hn n cng ln--> S ln. V d:
SH2O(r) ,SH2O(l)< SH2O (k) .
- S l hm trng thi v l i lng dung .
b. ngha thng k ca S
Trng thi ca mt tp hp bt k c th c c trng bng 2 cch:
- Bng gi tr ca cc tnh cht o c : T, P,C...--> c gi l cc thng s trng
thi v m.
- Nhng c trng nht thi ca cc phn t to nn h c gi l cc thng s vi
m.
* S thng s trng thi vi m ng vi mt trng thi v m c gi l xc sut nhit
ng
Nu s phn t trong h tng th S tng--> tng. Gia S v c quan h vi nhau
thng qua h thc Bolzomann.
H thc Boltzmann (l c s ca nguyn l III)
S=kln
k: hng s Boltzmann
Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng .
4.Bin thin entropi ca mt s qu trnh
a. Bin thin entropi ca qu trnh bin i trng thi ca cht nguyn cht
Trong sut qu trnh ny T=const ==> S ca mt mol cht nguyn cht trong qu
trnh bin i trng thi xy ra P=const l
2
S =
Q
T
H cf
H cf nhit chuyn trng thi
Tcf
b. Bin thin entropi ca qu trnh gin n ng nhit kh l tng

T=const, dn n n mol kh l tng t V1-->V2
2
S =
QTN
T
QTN
v T=const
T
V T=const --> U = 0 WTN = nRT ln
V2
V1
Theo nguyn l I: U = QTN + WTN = 0

==> S = nR ln
--> QTN = WTN = + nRT ln
V2
V1
V2
P
= nR ln 1
V1
P2
Nu P1>P2 --> S > 0 : qu trnh gin n ny t din bin

==> Cch pht biu khc ca nguyn l II: Cc cht kh c th t chuyn di t ni c p
sut cao n ni c p sut thp.
c. Bin thin entropi ca cht nguyn cht theo nhit :
un nng n mol 1 cht nguyn cht t nhit T1-->T2 vi iu kin trong khong
nhit cht ny khng thay i trng thi
- Trong iu kin P = const:
2
S p =
1
Q p
Vy S p = nC p
1
dH
dT
=
= nC p
T
T
T
1
1
dT
T
Trong iu kin V= const
2
S v =
Q v
dU
dT
=
= nC v
T
T
T
1
1
==> Vy S v = nC v
1
dT
T
Nu coi Cp hoc Cv khng i theo T th:

S p = nC p ln
T2
T1
S v = nC v ln
T2
T1
II. Nguyn l III ca nhit ng hc

Nhn xt: dng tinh th hon ho ca mt cht nguyn cht OK ng vi 1 trng thi
v m ch c 1 trng thi vi m ==> OK th = 1
1. Nguyn l III (tin Nernst)
Entropi ca mt cht nguyn cht di dng tinh th hon ho OK bng khng:
S (0 K ) = 0 = k ln
( = 1)
2.Entropi tuyt i ca cc cht nguyn cht cc nhit T

V d: un nng n mol 1 cht nguyn cht 0K -->T K, trong khong ny xy ra cc qu
trnh bin i trng thi v iu kin P=const. Tnh ST?
0 K---> Tnc--->Ts--->T
T
S = S T S T =0 = S T =
nC p
T =0
S = S T S T =0 =
nC
S
H nc
H s
dT
dT
dT
+n
+ nC p ( l )
+n
+ nC P ( h )
T
Tnc
T
TS
T
Tnc
TS
Tnc
0K
dT
T
p( r )
0
( J .K 1 .mol 1 )
thng th P=1atm, T=298K, n=1mol ==> S 298
-->Bng entropi chun ca cc cht 25oC

* Nhn xt: Gi tr S cht nguyn cht lun > 0, tr khi xt cho ion trong dung dch, c
th c Sion<0.
3.Bin thin entropy ca cc phn ng ho hc
V S l hm trng thi v l i lng dung nn:
S = S ( sp ) S ( tg )
( T, P =const)
Nu iu kin chun (P=1atm) v T=298K th:

0
0
S = S 298
(sp ) S 298
(tg )
V Skh>>Slng,Srn ==> c th cn c vo s mol kh 2 v ca phn ng nh

gi ln cng nh l du ca S ca phn ng.
n = 0 ==> S nh
n > 0 ==> S > 0 ==> phn ng tng S
n < 0 ==> S nh ==> phn ng gim S
V d:
SO2(k) + 1/2 O2(k) --> SO3(k) c n < 0 ==> S <0

c n = 0
C(gr) + O2(k) --> CO2(k)
==> S 0
III. HM TH NHIT NG. TIU CHUN XT CHIU CA QU TRNH

- H c lp: S 0 --> tiu chun t din bin v gii hn ca qu trnh
- H khng c lp: gm h + Mi trng --> av 1 h c lp mi bng cch gp
h v mi trng thnh 1 h c lp.
==> tiu chun t din bin v gii hn ca h mi l : S + S mt 0
S mt
cha xc nh nhng c th a v cc thng s ca h bng cch tm 1
hm thay th cho c ( S + S mt ), hm thay th ny gi l hm th nhit ng. Thng

gp h:
+ ng nhit, ng p ==> c hm th ng nhit ng p
+ ng nhit, ng tch==> c hm th ng nhit ng tch
1.Hm th ng nhit ng p
a. nh ngha: Xt 1 h: T, P = const
H thc hin mt bin i no
S + S mt = S +
H mt
H
= S
T
T
Mi trng
H mt = H h = H
H _Nhit lng trao i vi mi trng

S _Bin thin entropi ca h.
S mt =
H mt
H
=
T
T
==> tiu chun t din bin v gii hn ca qu trnh l:

S + S mt 0
<=> S
H
0
T
<=> H TS 0
<=> (H TS ) 0
t H-TS =G => G l hm trng thi
<=> G 0
G = H T S 0
: P,T=const ==> qu trnh t xy ra theo chiu G < 0 v
t cn bng khi G = 0
G c gi l : Nng lng Gibbs, Entanpi t do hay th ng p.
b. ngha vt l ca G
G = H TS = U +PV TS
dG = dU + pdV + VdP- TdS SdT
Nguyn l I => dU = Q + W , m dW = pdV + W ' ( W ' : cng hu ch)
=> dG = Q PdV + W '+ VdP + PdV TdS SdT
dG = Q + W '+ VdP TdS SdT
Nguyn l II => Q TdS ;
dU TdS PdV + W '
=> dG TdS + W '+ VdP TdS SdT

hay: dG W '+ VdP SdT
l phng trnh c bn ca nhit ng hc.
- Nu qu trnh l thun nghch-->cng l ln nht --> du =
dG = W ' max + VdP SdT
-
T v P =const => dT=0 v dP=0 c:

dG T , P = Wmax '
G T , P = W ' max
ngha ca G: G biu th cng hu ch ca qu trnh thun nghch ng nhit ng

p.
2. Hm th ng nhit ng tch (lm tng t G)
a. nh ngha: Xt 1 h T, V =const, h thc hin 1 bin i no
H
Mi trng
U _Nng lng trao i vi mi trng
S _Bin thin entropi ca qu trnh
U mt = U h = U
S =
U Mt
U
=
T
T
Tiu chun t din bin v gii hn ca qu trnh l:

S h + S mt 0
<=> S
U
0
T
<=> U TS 0
<=> (U TS ) 0 t U - TS = A => A l th ng tch ( nng lng Helmholtz).
<=> A 0
b. ngha A
A = U TS
dA = dU - TdS SdT ; dU = Q + W = Q PdV + W '
Q TdS
=>
dA TdS PdV + W ' TdS SdT
=> dA W ' PdV SdT

- Nu qu trnh l thun nghch-->cng l ln nht --> du =
dA = W ' max PdV SdT
-
T v V =const => dT=0 v dV=0 c:

dA = W ' max
A = W ' max
ngha ca A : Bin thin th ng tch A biu th cng c ch ca qa trnh

thun nghch ng nhit ng tch.
Tm li tiu chun t din bin v gii hn ca qu trnh l
T,P = const => dG 0
T,V = const => dA 0
Mi lin h gia G v A
G = H- TS U +PV TS =(U-TS) + PV =A + PV
Vy G = A+PV
3.Bin thin th ng p:
dG W '+ VdP SdT
dG 0
--> iu kin t din bin v gii hn

=> Qu trnh t din bin theo chiu lm gim G cho ti khi t gi tr Gmin: dG=0
(G=0)
d2G>0 (G>0)
a. Th ng p sinh chun ca 1 cht nhit T:
L s bin thin th ng p ca phn ng to thnh 1 mol cht t cc n cht
bn iu kin chun v nhit T ca phn ng.
K hiu: G T0, s (J.mol-1 hoc kJ.mol-1)
0
0
Thng T=298K => G 298
, s --> c bng th ng p sinh chun ca cc cht 25 C.
VD:
-1
0
G 298
, s ( NH 3 ) =-16,65kJ.mol ng vi qu trnh
-1
0
G 298
, s ( HCl ) =-95,5kJ.mol ng vi qu trnh
3
1
H 2 (k ) + N 2 (k ) NH 3 (k )
2
2
1
1
H 2 (k ) + Cl 2 (k ) HCl(k )
2
2
=> HCl(k) bn hn NH3(k) v nng lng to ra nh hn.

-
T nh ngha => GT0, s (n cht) =0
b. Tnh bin thin th ng p ca phn ng ho hc

V G l hm trng thi v l i lng dung nn c:
-
G p = G s (sp) G s (tg )
Nu iu kin chun v 250C c:

-
G p = G 0 s, 298 (sp ) G 0 s ,298(tg )

G thun=- G nghch
G <0: phn ng xy ra theo chiu thun

G =0: qu trnh cn bng
G >0; phn ng xy ra theo chiu nghch
- G T = H T TS T
0
0
0
G 298
= H 298
298.S 298
- GT = GT (cc qu trnh trung gian)

IV. CC YU T NH HNG N TH NG P
1. nh hng ca nhit
Xt h: ch c bin i thun nghch, khng sinh cng c ch, c P=const.
dG = W '+ VdP SdT , v W ' = 0 (khng sinh cng hu ch) v P=const
G
= S
T P
(G )
= S ,
T P
=>
nn
thay vo biu thc G = H TS ta c:
(G )
G = H + T
T P
(G )
G = H
T P
=> T
Chia c hai v cho T2 ta c:

(G )
T
G
T p
T
=>
H
G
= 2
T T p
T
H
T2
Phng trnh Gibbs-Helmholtz
H
T
hoc l
=
T
T2
Phng trnh Gibbs- Helmholtz cho php xc nh G theo T:

d(
G
H
) = 2 dT
T
T
thng xt iu kin chun (p= 1atm) v T=298K:

d(
G 0
H 0
0
) = 2 dT -> ly tch phn t 298-->T v thng thng bit gi tr G 298
v
T
T
H T0 = f (T )
H T
G 0
)=
dT
C: d (
2
T
298
298 T
T
==>
T
0
G T0 G 298
H T0
= 2 dT
298
T
298 T
H T0 = f ( T ) = a + bT + .....
=> G 0 = f (T )
2. nh hng ca p sut:
Xt h: bin i thun nghch, khng sinh cng hu ch, T=const.
T biu thc: dG = W '+ VdP SdT , W ' = 0 , T= const
G
=V
P T
P2
P1
nn c
=> dG = Vdp
P2
=> G T G T = Vdp
P2
P1
P1
i vi cht rn v cht lng --> coi V=const khi P bin i ( tr min P ln) nn
: G T G T = V( P2 P1 )
P2
P1
G TP 2 = G TP1 + V( P2 P1 )
hay G = V( P2 P1 )
i vi cht kh (coi l kh l tng) --> V =
P2
G TP 2 G TP1 = nRT
P1
Vy: G = nRT ln
nRT
P
P
dP
= nRT ln 2
P
P1
P2
P1
hay G T = G T + nRT ln
P2
P1
P2
P1
Nu ban u P1=1atm (iu kin chun) th G T = G T0

P2
G T = G + nRT ln P
0
T
VD: Nn 0,5 mol kh l tng t P=1atm n P= 2atm 250C. Hi qu trnh nn c t

xy ra c khng?
G = nRT ln
P2
2
= nRT ln > 0
1
P1
==> qu trnh nn khng t xy ra.

3. nh hng ca thnh phn cc cht. Khi nim th ho
Xt h gm i cht: i = 1, n vi s mol tng ng l n1, n2, ...ni.
G=G(T, P, n1, n2...ni)
dG = (
G
G
G
) P , N dT +
dP +
T
P T , N
n1 T ,, P,, n
G
G
dn1 +
dn 2 + ... +
n1 T ,, P,, n j 2
n i
j 1
dn i
T , , P ,, n j i
dG = SdT + Vdp + W '
Ch s N ch ra rng n1,n2, n3...ni l khng i, ch s nj#i ch ra rng ch c ni l bin i.

G
= Gi = i
ni T ,, P ,,n j i
t:
Trong : G i th ng p mol ring ca cht i trong h
i Th ho ca cht i
==> W ' = i dn i => i dn i l 1 dng cng hu ch ==> gi l cng ho

T : dG = VdP SdT + i dn i
* ngha vt l ca i :
-
Th ho ca cht i ( i ) l th ng p mol ring phn ca i trong hn hp
i l tng kh nng sinh cng hu ch ca h khi thm 1 lng v cng nh
cht i vo h trong iu kin P,T v thnh phn (s mol) ca cc cht khc l khng i.
i c tnh cho 1 mol cht.
i l i lng cng nhng dni l i lng dung
dn
i
c th lm tiu chun xt chiu v gii hn trong iu kin T,P khng
i:
dn <0: Qu trnh t din bin

+ dn =0: Qu trnh cn bng
+
Phn ng xy ra theo chiu gim th ho.

* Mt vi tnh cht ca th ho:
i = Gi
--> i ph thuc vo T, P (ging Gi)
Nu h ch gm 1 cht kh th th ho chnh l th ng p ca 1 mol cht: G= .

G
= =V
P T P T
do :
T lm tng t nh hm G, s thu c phng trnh ca T (ging GT):

T = T0 + RT ln P
T0
P(atm) (i vi 1 mol kh).
: th ho chun ca cht kh nhit T, P=1atm v tnh cho 1 mol.
Nu h gm 1 hn hp kh c p sut chung l P th p sut ring phn ca kh i

trong hn hp l Pi=Ni.P ( vi N i =
ni
)
ni
i ( T ) = i0( T ) + RT ln Pi = i0( T ) + RT ln(N i P )

i ( T ) = i0( T ) + RT ln P + RT ln N i
=> i ( T ) = i0( T , P ) + RT ln N i
-
i vi phn ng ho hc: aA + bB --> cC + dD

G p = i (sp ) i (tg )
iu kin chun:
G p0 = i0 (sp ) i0 (tg )
Vy trong iu kin ng nhit, ng p:
(sp) < (tg) : phn ng t din bin (t tri qua phi)

+Nu (sp) = (tg ) phn ng trng thi cn bng
+ Nu
=> th ho cng l tiu chun xt chiu v gii hn ca cc qu trnh (phn ng xy ra

theo chiu gim th ho)
4.Mi quan h gia du G v ln H , S v T:
T=const --> G T = H T TS T
G < 0
: Qu trnh t xy ra
<=> H < 0 : chiu tng bn lin kt

S > 0 : chiu tng hn lon
STT
Du H
Du S
Du G
Phn ng t xy ra mi nhit
Phn ng khng t xy ra mi nhit
Phn ng t xy ra nhit thp
phn ng t xy ra nhit cao
D on chiu
V d:
- phn ng: CaCO3(r) <=> CaO(r) + CO (k)
H p0 = +178,22kJ
n = 1 > S > 0 --> phn ng ch xy ra nhit cao

H p0 = 99,12kJ
- phn ng: SO2(k) + 1/2 O2 (k) --> SO3(k)
n = 0,5 > S < 0 --> phn ng xy ra nhit thp, nhng nu thp qu th vn
tc khng ln --> phn ng khng xy ra ngay c

==> iu kin: nhit khng qu thp
Ti liu tham kho:

CHNG III: CN BNG HO HC

I.PHN NG THUN NGHCH V PHN NG 1 CHIU
1.Phn ng thun nghch

L phn ng xy ra theo hai chiu tri ngc nhau trong cng mt iu kin (c
im ca phn ng thun nghch: khng tin hnh n cng m dn n cn bng)
V d: N2O4(k) <=> 2NO2(k)
Khi ly kh NO2 (hoc N2O4) nghin cu --> lun thu c ng thi c kh N2O4
(hoc NO2) trong bnh ngay nhit thng do tn ti s chuyn ho gia hai kh trn -> gi phn ng trn l phn ng thun nghch.
2.Phn ng 1 chiu: L phn ng ch xy ra theo mt chiu xc nh
V d: Phn ng phn hu KClO3(xc tc MnO2) : KClO3 --> KCl + 3/2O2
c im: tin hnh ti cng
3.Trng thi cn bng ho hc
Mt phn ng khi t trng thi cn bng th:
Xt v mt ng hc: vt=vn
-
Xt v mt nhit ng: G p = 0
* Vy trng thi cn bng ho hc: l trng thi ca phn ng thun nghch khi tc
phn ng thun bng tc phn ng nghch (hoc khi bin thin th ng p bng
khng).
* c im ca trng thi cn bng ho hc:
- L cn bng ng (phn ng vn xy ra theo 2 chiu ngc nhau nhng vt=vn).
-Ti trng thi cn bng thnh phn ca cc cht khng thay i: cht tham gia
phn ng mt i bao nhiu theo phn ng thun th li c sinh ra by nhiu theo phn
ng nghch).
- Trng thi cn bng ch tn ti khi cc iu kin thc hin phn ng (C, t0,p)
khng i.
II.PHNG TRNH NG NHIT VANT HOFF. HNG S CN BNG K
1.Thit lp phng trnh ng nhit Vant Hoff

Xt phn ng:
aA + bB <=> cC + dD
T=const v A,B,C,D l cc kh l tng
Ta c: G T = i (sp) i (tg ) = (c C + d D ) (a A + b B )
M: i ( T ) = i0( T ,) + RT ln Pi (i vi 1 mol)
=> c C ( T ) = c C0 ( T ) + cRT ln PC = c C0 ( T ) + RT ln PCc (cho c mol)
Tng t:
B (T )
= b
0
B (T )
+ RT ln P Bb :
d D ( T ) = d D0 ( T ) + RT ln PDd
a
A(T )
= a
0
A(T )
+ RT ln P Aa
=>
G T = [(c C0 ( T ) + RT ln PCc ) + (d D0 ( T ) + RT ln PDd )] [(a A0 ( T ) + RT ln PAa ) + (b B0 ( T ) + RT ln PBb )]
PCc .PDd
G T = [(c (C) + d ( D) (a ( A) + b ( B )] + RT ln a b
PA .PB
0
T
0
T
PCc .PDd
G T = G + RT ln a b
PA .PB
0
T
0
T
0
T
bd
bd
Pi: p sut ring phn ca cc cht kh i= A,B,C,D)

PCc .PDd
t a b
PA .PB
=P
bd
=> G T = G T0 + RT ln P
(*)
PCc .PDd
- Ti trng thi cn bng==> G T = 0 => G = RT ln a b
PA .PB
0
T
PCc .PDd
t: a b
PA .PB
cb
= K p = const T=const (v trng thi cn bng, thnh phn cc
cb
cht khng bin i na)

==> G T0 = RT ln K P
v GT = RT ln
(**)
(***)
KP
G T , , G T0 (J)
Trong :
R=8,314J.K-1mol-1
P (atm)
Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh
ng nhit Vant Hoff
2.Phng trnh hng s cn bng K:
a.Hng s cn bng Kp
PCc .PDd
K p = a b
PA .PB
cb
Pi: p sut cc kh trng thi CB
KP khng c n v.
Kp ch ph thuc vo bn cht phn ng v nhit .
i vi 1 phn ng xc nh, T=const --> Kp=const --> gi l hng s cn
bng ca phn ng.
b.Cc hng s cn bng khc
CCc .C Dd
* K C = a b
C A .C B
cb
Ci: nng mol/lit cc cht trng thi cn bng
KC ph thuc vo bn cht phn ng v nhit .

i vi 1 phn ng xc nh --> KC =f(T): KC ch ph thuc vo nhit
n c .n d
* K n = Ca Db
n A .n B cb
ni; s mol kh i trng thi cn bng
Kn ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng v tng s mol

kh ca h khi cn bng
N c .N d
* K N = Ca Db Ni: nng phn mol ca kh i: N i = i

ni
N A .N B cb
KN ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng
c.Mi quan h gia cc hng s cn bng
- Ta c PiV=niRT (V th tch hn hp kh (lt))
=> Pi =
KP
n i RT
= Ci RT
V
(CC RT )c (C D RT )d
=
(C B RT )b (C A RT )a
thay vo phng trnh Kp ta c

=
CCc .C Dd
b
B
C .C
a
A
RT [(c + d )(b + a )] = K c .( RT ) n
n = s mol kh sn phm- s mol kh tham gia (da vo phng trnh phn ng)
Vy
(vi R= 0,082 atm.l.mol-1K-1)
K P = K c .( RT ) n
-Mt khc ta c:
Pi = N i .P =
ni
.P --> thay vo Kp ta c:
ni
K P = K N .Pcbn
KP
= K n .
P
ni
cb
( n i )cb tng s mol kh c mt trong h phn ng khi cn bng.

Vy c:
K P = K C ( RT ) n = K N .Pcbn
P
= K n .
n
i
cb
*Nhn xt:
- Khi n = 0 (tng s mol kh 2 v phn ng bng nhau) --> Kp=KC=Kn=KN=K=f(T)
- i vi 1 phn ng cho th:
+ Kp,KC ch ph thuc vo nhit
+ KN ph thuc vo nhit , P chung ca h khi cn bng
+Kn ph thuc vo T,P chung ca h khi cn bng, tng s mol kh ca h khi cn

bng.
* Ch :
- Gi tr hng s cn bng K ca phn ng u phi gn vi 1 phn ng c th no .
KP =
V d: SO2(k) + 1/2O2(k) <=> SO3(k)
2SO2(k) + O2(k) <=> 2SO3(k)
K' P =
SO3(k) <=> SO2(k) + 1/2O2(k)
K =
PSO3
1
PSO2 .PO22
PSO2 3
2
SO2
.PO2
= K P2
''
P
PSO2 .PO22
PSO3
= K P1
- Nu K c gi tr kh ln --> coi phn ng xy ra hon ton, K nh -> phn ng thun

nghch.
- Nu phn ng c cht rn hoc cht lng tham gia (v khng tan ln vo cc cht khc)
th chng khng c mt trong phng trnh hng s cn bng ( v i ( T ) = i0( T ) trong
sut qu trnh phn ng--> khng cn RTlnPi)
V d: Fe2O3(r) + 3 CO(k) <=> 2Fe(r) + 3 CO2(k) Kp=
3
PCO
2
3
PCO
KP =
Hg(l) + 1/2 O2(k) <=> HgO(r)
1
1
PO22
3. Cc phng php xc nh hng s cn bng

a.Xc nh theo thnh phn cc cht ti thi im cn bng
V d: CaCO3(r) <=> CaO(r) + CO2(k)
Nung CaCO3 nhit T , khi cn bng: PCO = 740mmHg .Tnh Kp
2
Gii:
K P = PCO2 =
740
760
b.Xc nh thng qua 1 s i lng nhit ng

G T0 = RT ln K P
G T0
RT
==> K P = exp
V d: Tnh Kp ca phn ng sau 250C:

2NH3(k) <=> N2(k) + 3H2(k)
0
1
bit G 298
,s (NH 3 ) = 16,65kJ .mol
Gii:
0
0
1
G 298
= 2G 298
,s (NH 3 ) = ( 2)( 16,65) = +33,3kJ .mol
0
G 298
33,3.10 3
= exp
= 1,45.10 6
K P = exp
8,314.298
R.298
c. Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn
V d:
KP=?
O2(k)
Cgr
K1
CO2(k)
K2
CO(k)
1/2 O2(k)
G 0 = G10 + G 20
RT ln K P = ( RT ln K 1 ) + ( RT ln K 2 )
lnKP=lnK1+lnK2
==> K=K1.K2
III.S CHUYN DCH CN BNG. NGUYN L LE CHATIELIER
1.S chuyn dch cn bng

- Xt v mt nhit ng, khi phn ng t trng thi cn bng--> G = 0 -->
P
KP
= 1 khi
h ang trng thi cn bng nu ta thay i mt trong cc thng s trng thi (P,T,C)
ca h --> G 0 => cn bng b ph v, qu trnh s tin hnh theo chiu G < 0 t
ti trng thi cn bng mi ng vi cc thng s mi (P,T,C).
- Xt v mt ng hc, khi phn ng t trng thi cn bng --> vt=vn => v=0. Khi h
t trng thi cn bng, ta thay i 1 trong cc thng s trng thi (P,C,T) => vt vn ==>
qu trnh tin hnh theo chiu v > 0 t trng thi cn bng mi ng vi cc thng
s mi.
==> gi l s chuyn dch cn bng.
nh ngha: S chuyn dch cn bng l s chuyn t trng thi cn bng ny sang trng
thi cn bng khc di nh hng ca cc tc ng bn ngoi (P,T,C) ln h.
2.nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant
Hoff
Xt phn ng: aA + bB <=> cC + dD
P=const
G T0
Ta c: ln K P =
RT
Mt khc:
GT0
ln K P
T
do : =>
H 0
= 2T
T
P
H T0
=
2
P RT
=> phng trnh ng p Vant Hoff
- Nu H T0 > 0 (phn ng thu nhit) --> hm ng bin

+ Khi nhit tng --> Kp tng --> cn bng chuyn dch theo chiu thun ( chiu
thu nhit)
+ Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu nghch ( chiu
to nhit)
- Nu H T0 < 0 (phn ng to nhit) --> hm nghch bin:
+Khi nhit tng --> Kp gim --> cn bng chuyn dch theo chiu nghch (
chiu thu nhit)
+Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu thun ( chiu to
nhit)
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi:
+ Khi nhit tng th cn bng chuyn dch theo chiu lm gim nhit ca h
l chiu thu nhit c H T > 0
+ Khi nhit gim th cn bng chuyn dch theo chiu lm tng nhit ca h
l chiu to nhit c H T < 0
* T phng trnh Vant Hoff suy ra:
H T0
ln K P =
RT 2
.T
Nu trong khong nhit T1-->T2 hp -->c th coi H T0 = const th:

H 0
=
d
ln
K
P
R
T1
T2
=> ln
K PT
K PT
T2
dT
T1
H 0 1 1

=
R T1 T2
vi H 0 (J) v R=8,314 J.K-1mol-1

3. nh hng ca p sut n s chuyn dch cn bng
Ta c: K P = K N .Pcbn
V Kp khng ph thuc vo P--> thay i P th Kp=const nn:
- Nu n > 0 : khi tng P--> KN gim ( gi Kp=const) => chuyn dch cn bng theo
chiu nghch ( lm gim s mol kh) v ngc li
- Nu n < 0 : khi tng P--> KN tng ( gi Kp=const) => chuyn dch cn bng theo
chiu thun ( lm gim s mol kh) v ngc li khi P gim --> KN gim --> cn bng
dch chuyn theo chiu nghch ( lm tng s mol kh)
- Nu n = 0 => P khng nh hng ti s chuyn dch cn bng
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi:
Nu P tng => cn bng chuyn dch theo chiu P gim (gim s mol kh
n < 0 )
Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh
n > 0 )
4. nh hng ca nng
Xt phn ng: aA + bB <=> cC + dD
C c .C d
c K C = Ca Db = const T=const
C A .C B cb
- Nu tng CA, CB => cn bng chuyn dch theo chiu tng CC,CD ( gi KC=const) =>
cn bng chuyn dch theo chiu thun lm gim CA,CB
- Nu gim CA, CB => cn bng chuyn dch theo chiu gim CC,CD ( gi KC=const)
=> cn bng chuyn dch theo chiu nghch lm tng CA,CB
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li thay i bn ngoi.Nu
tng Ci th cn bng chuyn dch theo chiu lm gim Ci v ngc li.
5. Nguyn l chuyn dch cn bng Le Chatelier
Khi mt h ang trng thi cn bng, nu ta thay i 1 trong cc thng s trng
thi ca h ( T, P hoc C) th cn bng s chuyn dch theo chiu chng li s thay i
.
Ti liu tham kho:

Chng IV: Cn bng pha

I. Mt s khi nim
1. Pha ( ) l phn ng th ca h c thnh phn, tnh cht l hc , tnh cht ho hc
ging nhau mi im ca phn ng th v c b mt phn chia vi cc phn khc

ca h.
- Pha ch gm 1 cht gi l pha nguyn cht (pha n) cn pha gm 2 cht tr ln--> gi
l pha phc tp.
- H gm 1 pha --> h ng th.
- H 2 pha -> h d th.
V d: H gm H2O + H2O lng + H2O hi => gm 3 pha: rn, lng, hi.
H gm CaCO3(r), CaO(r),CO2(k) --> 3 pha: 2 fa rn + 1 pha kh
2. Cu t: L phn hp thnh ca h c th c tch ra khi h v tn ti c bn ngoi
h.
S cu t trong h k hiu l R
V d: dung dch NaCl gm 2 cu t l NaCl v H2O --> R=2
3.S cu t c lp (K): L s ti thiu cc cu t xc nh thnh phn ca tt c
cc pha trong h.
- Nu cc cu t khng phn ng vi nhau v nu pha c thnh phn khc nhau th K=R
(trong h khng c phng trnh lin h nng cc cu t)
V d: dung dch NaCl => R=K=2.
-Nu cc cu t tng tc vi nhau v nm cn bngvi nhau--> chng khng cn c lp
vi nhau na--> K=R-q
q: s h thc lin h gia cc nng ( q c th l phng trnh hng s cn bng, iu
kin u v nng ca cc cu t)
V d: H gm 3 cu t HCl, Cl2, H2 u l cc cht kh c tng tc,nm cn bng vi
+ Cl2(k)
nhau: 2HCl(k)
<=> H2(k)
KC =
[H 2 ][Cl2 ]
[HCl]2
=> bit c nng ca 2 cu t s bit c nng
ca cu t cn li.
Vy h c: R=3, q=1, ==> K= R-q=2
Nu gi thit ban u h ch c HCl ( hoc cho t l mol H2:Cl2 ban u) => q=2 => K=1
4.Bc t do ca h(C): L s ti thiu cc thng s trng thi cng (P,T,C) xc
nh trng thi cn bng ca 1 h ( l s thng s trng thi cng c th thay i
1cch c lp m khng lm bin i s pha ca h)
V d:
H2O(l) <=> H2O(k)
==> cn bng c 2 pha==> C=1 v
+ C th thay i 1 trong 2 thng s P hoc T m khng lm thay i s pha ca
h.
+ Hoc: mt nhit xc nh th P hi H2O nm cn bng vi H2O lng l xc

nh, tc l ch cn bit 1 trong 2 thng s T hoc P th xc nh c trng thi cn bng
ca h.
5.Cn bng pha: Cn bng trong cc h d th, cc cu t khng phn ng ho hc
vi nhau nhng xy ra cc qu trnh bin i pha ca cc cu t => cn bng pha.
II. Quy tc pha Gibbs.
Xt h gm R cu t 1,2,....R c phn b trong pha ( , , ,..., pha)

1.iu kin cc pha nm cn bng vi nhau: m bo cc cn bng sau:
- Cn bng nhit: nhit cc pha bng nhau
T = T = T = ... = T
-Cn bng c: p sut cc pha bng nhau

P = P = P = ... = P
-Cn bng ho: th ho ca mi cu t trong cc pha bng nhau:

i = i = i = ... = i
2.Qui tc pha Gibbs

- Cc thng s trng thi cng xc nh trng thi ca h l T,P, C
Gi Ni l nng mol phn ca cu t i trong 1 pha th N1+N2+N3+...+Ni=1
=> Vy xc nh nng ca R cu t trong 1 pha cn bit nng ca (R-1) cu
t.
V c pha => xc nh nng ca R cu t trong pha th s nng cn
bit l (R-1).
T s thng s trng thi cng xc nh trng thi ca h l
(R-1)+ 2
trong s 2: biu th 2 thng s bn ngoi l T v P xc nh trng thi ca h
V cc pha nm cn bng vi nhau => cc thng s khng c lp vi nhau na: c lin
h vi nng m khi cn bng th ca mi cu t trong cc pha phi bng nhau ( iu
kin cn bng ho)
1 ( ) = 1 ( ) = ... = 1 ( )
2 ( ) = 2 ( ) = ... = 2 ( )
R ( ) = R ( ) = ... = R ( )
=> Mi cu t c ( -1) phng trnh lin h ==> R cu t c c R( -1) phng trnh

lin h gia cc thng s.
Nu c thm q phng trnh lin h nng cc cu t, v d: khi c phn ng ho hc
gia cc cu t th s phng trnh lin h cc thng s trng thi cng ca h l:
R( -1) + q
Bc t do ca h = Cc thng s trng thi s phng trnh lin h gia cc thng s

C= [ (R-1)+2]-[R( -1)+q]
C=R-q- +2
C= K - q + 2
=> Biu thc ton hc ca quy tc pha Gibbs
* Nhn xt:
+ Khi K tng, => C tng, tng v C gim.
+ Bc t do C 0 K + 2
+Nu trong iu kin ng nhit hoc ng p th: C =K - + 1 (Nu phng trnh
c n = 0 => P khng nh hng ti phn ng --> dng phng trnh ny)
+Nu h va ng nhit va ng p th C=K-
V d1: Xt h 1 cu t (R=K=1), v d nc nguyn cht
- Nu trng thi hi => =1 => C= K- +2= 1-1+2=2 => trng thi ca hi nc c
xc nh bi 2 thng s trng thi cng l T v P
- Nu hi nc nm cn bng vi nc lng th =2=> C=1-2+2=1 => trng thi ca h
gm H2O lng v hi c xc nh bi 1 trong 2 thng s l T hoc P ( v 1nhit
xc nh th P ca hi nc l xc nh)
V d2: Xt h gm: Mg(OH)2 (r) <=> MgO (r) + H2O(k)
=2 pha rn + 1 pha kh =3 pha
C=R-q+2=3-1-3+2=1
=> c php thay i 1 trong 2 thng s l T hoc P m khng lm thay i s pha ca
h hoc trng thi cn bng c xc nh bng 1 trong 2 thng s T hoc PH O(h )
2
III.Cn bng pha trong h 1 cu t

1.Cn bng pha trong h 1 cu t
Xt h gm 1 cht nguyn cht, khi trong h c 2 pha nm cn bng nhau:
Rn(R) <=> Lng(L)
Lng(L)<=>Hi (H)
Rn (R)<=>Hi (H)
( R ( ) R ( ) ) => v h 1 cu t, s pha 3 (3 K + 2 )
=> C= K- +2 =1-2+2 =1 (R=K-1) trng thi cn bng gia hai pha c c trng
bi hoc T hoc P, tc l nu 1 trong 2 thng s trng thi l P hoc T bin i th thng
s kia phi bin i theo: p=f(T) hoc T=f(P). C th l :
- P=const=> cht nguyn cht nng chy, si hoc chuyn trng thi tinh th 1 nhit
nht nh, c gi l nhit chuyn phaTcf, nhit ny khng b bin i trong
sut qu trnh chuyn pha. Khi p sut thay i => Tcf thay i theo.
Vd: P=1atm, nc nguyn cht ng c 00C v si 1000C
P=2atm, nc nguyn cht ng c 0,00760C v si 1200C
- T=const, hi nm cn bng vi lng v rn c P nht nh gi l P hi bo ho (hi

c goi l hi bo ho)
Cc ng cong biu th s ph thuc ca Phi bo ho ca pha rn vo nhit , ca pha lng
vo nhit v nhit nng chy vo P ct nhau ti 1 im gi l im ba, im ba
ny ba pha rn lng hi (R, L, H) nm cn bng vi nhau:
R
Khi C=1-3+2 =0 => v tr im ba khng ph thuc vo T v P m ch ph thuc vo

bn cht cht nghin cu.
2. nh hng ca p sut n nhit nng chy, si v chuyn dng tinh th ca
cht nguyn cht
V h 1 cu t nn th ha ng nht vi th ng p mol (Gi= i ). Khi T, P khng i
iu kin cn bng gia hai pha v l:
G ( ) = G ( )
V h c C=1 nn nu mt thng s bin i, v d, p sut bin i mt lng dP th
mun hai pha tn ti cn bng, nhit cng phi bin i mt lng dT. Khi th
ng p mol phi bin i:
G ( ) > G ( ) + dG ( )
G ( ) > G ( ) + dG ( )
Sao cho: G ( ) + dG ( ) = G ( ) + dG ( ) => dG ( ) = dG ( )
Thay vo cng thc: dG= VdP SdT ta c:
V ( ) dP S ( ) dT = V ( ) dP S ( ) dT
dT V ( ) V ( ) V
=
=
=>
S
dP S ( ) S ()
H
C S =
suy ra:
T
dT Tcf V
=
phng trnh Clapeyron
dP H cf
Trong H c tnh bng J th V tnh bng m3, T bng K v P bng Pa.
- Khi mt cht si th V =Vh- Vl >0 v H hh>0 (hh:ha hi), nn p sut bn
ngoi tng th nhit si tng theo.
- Khi nng chy H nc >0 v a s trng hp V = Vl-Vr >0, do P tng th
nhit nng chy tng. i vi nc Vl<Vr nn V <0 ngha l p sut tng
th nhit nng chy ca nc gim.
3. nh hng ca nhit n p sut hi bo ho ca cht nguyn cht

Xt cc trng hp: L <=> H
R <=> H
V Vr,Vl << Vh => V = Vh Vl Vh v V = Vh Vr Vh
Nu hi c coi l kh l tng,xt i vi 1 mol c:
Vh =
RT
thay vo phng trnh Clayperon c:
P
H cf H cf
dP H cf
=
=
=
.P
dT Tcf .V Tcf .V Tcf2 .R
=>
dP H
=
dT
P RT 2
d ln P H
=
dT
RT 2
(v
dP
= d ln P ) nn c:
P
-> phng trnhClaypeyron-Clausius
Trong khong nhit hp -> c th coi H = const khi c

ln
P2 H 1 1

=
P1
R T1 T2
(*)
P1,P2 : cng n v
R=8,314J.K-1.mol-1
H : J
Biu thc (*) cho bit c th:

- Tnh p sut hi bo ho nhit T2(hoc T1) khi bit P nhit T1 v H cf
- Tnh nhit si P bt k khi bit nhit si mt p sut no v H bay hi.
Tnh H bng cch o P1 v P2 2 nhit khc nhau.
Ti liu tham kho:

Chng V Dung dch

I.H phn tn
1.nh ngha: L h gm 2 hay nhiu cht trong cht ny c phn b trong cht kia
di dng nhng ht rt nh.
- Cht phn b c gi l cht phn tn, cht kia l mi trng phn tn. Cht phn tn
v mi trng phn tn c th 1 trong 3 trng thi: rn, lng hay hi.
Vd: ng tan trong nc => ng l cht phn tn, H2O l mi trng phn tn
- Da vo kch thc ca ht phn tn, chia lm 3 h phn tn:
a.H phn tn th: Kch thc ht t 10-7-10-4m
-c im: Khngbn,cht phn tn d tch ra khi mi trng phn tn.
-C 2 dng:
+ Huyn ph: cht phn tn l rn, pha phn tn l lng. v d: nc ph sa
+ Nh tng: cht phn tn l lng, mi trng phn tn cng l lng v d: sa c
ln nhng ht m l lng
b.Dung dch keo: (H keo): Kch thc ht t 10-7 10-9m
- c im: tng i bn
c. Dung dch thc (dung dch): Kch thc ht 10-10m (bng kch thc phn t hoc
ion), trong cht phn tn v mi trng phn tn c phn b vo nhau di dng
phn t hoc ion, gia chng khng cn b mt phn chia, to thnh 1 khi ng th gi
l dung dch thc
Cht phn tn c gi l cht tan, mi trng phn tn c gi l dung mi
-c im: H ny rt bn
2.Cc loi nng
-Nng % (C%): l t l % khi lng cht tan so vi khi lng dung dch (C%chnh l
lng cht tan c trong 100g(100kg) dung dch)
C% =
a
.100 %
a+b
a,b lng cht tan v lng dung mi, tnh bng g (kg)
-Nng mol/lit (CM): l s mol cht tan c trong 1 lit dung dch
-Nng ng lng (CN):S mol ng lng cht tan c trong 1 lt dung dch
-Nng molan ( ) l s mol cht tan c trong 1000gam dung mi
-Nng phn mol: N i =
ni
ni
II. ng lng ()
Trong cc phn ng ho hc, cc cht tc dng va vi nhau theo nhng s phn khi
lng tng ng gi l ng lng.
Chn ng lng ca H lm n v H=1
1.nh ngha nglng
- ng lng ca mt cht hoc ca 1 nguyn t l phn khi lng ca cht hoc
nguyn t tc dng va vi 1 ng lng ca H.
V khng phi mi cht u phn ng vi H => nh ngha c m rng nh sau:
ng lng ca 1 nguyn t hay 1 hp cht l s phn khi lng ca n tc dng va

vi 1 ng lng ca 1 cht bt k
V d:
Cl2 + H2 = 2HCl
Cl2 + Zn =ZnCl2
=> 71 phn khi lng ca Cl2 tc dng vi 2 phn khi lng ca H
Vy kt hp vi 1 ng lng ca H ch cn 1 khi lng ca Cl2 bng khi lng
nguyn t ca n => Cl=35,5, Zn= 32,5
-Mol ng lng ca mt cht: l khi lng tnh ra g c gi tr ng bng ng lng
V d: O=8g
2.Cch tnh ng lng
a.ng lng ca nguyn t
=
A
n
A: khi lng nguyn t nguyn t

n: ho tr nguyn t
Vi nguyn t
c nhiu ho tr
khc nhau s c nhiu ng lng v ng lng ca chng gn vi 1 phn ng c th
m chng tham gia.
b.ng lng ca hp cht
=
M
n
M: khi lng phn

n: tu tng trng hp
Cch xc nh n
- i vi phn ng oxi ho kh: n l s e trao i ng vi 1 phn t cht (n l s
e m 1 phn t trao i trong phn ng)
- i vi phn ng trao i: n l s in tch (+) hoc (-) m 1 phn t cht trao
i trong phn ng
=
NaHSO4
+ H2O
(1)
V d:
H2SO4 + NaOH
H 2 SO4 (1) =
NaOH (1) =
M H 2 SO4
1
M NaOH
1
98
= 98
1
40
=
= 40
1
=
H2SO4 + 2NaOH
H 2 SO4 ( 2 ) =
M H 2 SO4
NaOH ( 2 ) =
M NaOH
1
Na2SO4
+ H2O
(2)
98
= 49
2
40
=
= 40
1
=
i vi trng hp tnh ng lng ca mt cht khng c phn ng c th th:

=
M
n
+ i vi axit: n l s H axit trong phn t

+ i vi baz: n l s nhm OH- baz trong phn t
+ i vi mui: n l s in tch (+) hoc in tch (-) m cc ion mang

trong 1 phn t.
V d: Na SO =
2
M Na2 SO4
2
Al2 ( SO4 )3 =
+Mi quan h gia CM v CN:
M Al2 ( SO4 )3
CM=
6
CN
n
3.nh lut ng lng

Cc cht tc dng va vi nhau theo cc khi lng t l vi ng lng ca chng.
=>
mA A
=
mB B
=>
mA mB
=
=> n ng lng cht A phn ng va vi n ng lng cht B ( S
A B
mA l khi lng cht A tc dng va vi khi lng mB cht B
ng lng cht A bng s ng lng cht B)

=> Nu c VA(l) cht A nng mol ng lng l C N phn ng va vi VB(l) cht
A
B nng mol ng lng l C N th

B
VA. C N =VB. C N
A
-> ng dng nhiu trong chun th tch
V d: trung ho 25ml NaOH cn 28ml dung dch axit 0,1N => tnh lng NaOH c
trong 1l dung dch ?
Gii
Gi x l nng ng lng mol ca NaOH
=> x.25=0,1.28
=>x=28.0,1/25
NaOH=40=> s g NaOH c trong 1 lt dung dch l
m=40.x=40.28.0,1/25=4,48g
III. ho tan
1.Qu trnh ho tan. Nhit ho tan ca mt cht
Qu trnh ho tan (khng phi l qu trnh trn ln) gm qu trnh
+ Qu trnh phn tn cht tan( di dng nguyn t, phn t,ion) vo trong khp
th tch dung mi.
+Qu trnh tng tc gia cc phn t ca dung mi vi cc phn t ca cht tan
=> to thnh dung dch (hp cht ho hc)
Hp cht ho hc to thnh gi l hp cht sonvat, nu dung mi l nc th gi l hp
cht hydrat.
=> Qu trnh ho tan c s ph v lin kt cng loi to lin kt khc loi v c th
biu din bng s :
H ht
+
dm
T+T +
dm
T_T
T_dm
H pt > 0
Trong :
H sv < 0
T cht tan
dm dung mi
H pt nng lng phn tn ( cn tiu tn -> H pt > 0 )
H sv nng lng qu trnh sovat (Qu trnh l to nhit --> H sv < 0 )
(Nu dung mi l nc -> H sv = H h nhit hidrat ho)

H ht nhit ho tan
Theo s trn ta c:
H ht = H pt + H sv
(do H sv < 0 , H pt > 0 --> H ht c th m hoc dng)
+Nu H pt > H sv H ht > 0 : qu trnh ho tan thu nhit, l qu trnh ho tan

ca a s cht rn vo trong nc.
+Nu H pt < H sv H ht < 0 :qu trnh ho tan to nhit, l qu trnh ho tan
ca a s cht kh vo trong nc.
+Nu H pt = H sv H ht = 0 : Trn ln l tng ( i vi dung dch l tng)
- nh ngha nhit ho tan ca mt cht: L lng nhit to ra hay thu vo khi ho tan 1
mol cht vo 1 lng dung mi ln nhit v P xc nh.
Vd: Khi ho tan 1 mol CaCl2 vo H2O thot ra 1 nhit lng l 72,802 kJ, vy
H ht (CaCl 2 ) = 72,802kJ .mol 1
ha tan: Qu trnh ha tan: cht tan + dm <-> dung dch l mt qu trnh thun
nghch, khi t cn bng cht tan khng tan thm na to thnh dung dch bo ha.
- ha tan ca mt cht c tnh bng nng ca dung dch bo ha cht
iu kin cho v k hiu l s.
- S c th biu din bng mi cch biu din nng .
- ha tan s ca mt cht ph thuc vo:
+ Bn cht ca dung mi v cht tan.
+ Nhit
+ p sut: (nu cht tan l cht kh).
a. nh hng ca bn cht cht tan v dung mi n s
- Cc cht c cu to phn t tng t nhau d ha tan vo nhau, phn t dung mi
phn cc ln th ha tan tt cc cht phn cc v ngc li.
- VD: Dung mi l H2O l phn t phn cc ch ha tan cc cht m fn t phn
cc hoc hp cht ion nh HCl, NaCl..
H2O t ha tan I2 v I2 khng phn cc
Benzen khng phn cc benzen thc t khng tan trong H2O.
I2 tan tt trong benzen c mu tm.
C th ng dng tnh cht ny trong tch, chit hu c.
b. nh hng ca nhit ti tan
CT + Dm <=> Dd , H ht
-
Nu H ht >0 (ha tan a s cc cht rn):
+ Khi nhit tng -> cn bng chuyn dch theo chiu thun tan
tng.
+ Khi nhit gim -> cn bng chuyn dch theo chiu nghch tan
gim.
Trong mt s trng hp c th iu ch dung dch qu bo ha c nng ln hn
ha tan s nhit T dung dch qu bo ha khng bn.
- Nu H ht <0 (ha tan a s cht kh)
+ Khi nhit tng -> cn bng chuyn dch theo chiu nghch tan
gim.
+ Khi nhit gim -> cn bng chuyn dch theo chiu thun tan
tng.
c. nh hng ca P (i vi cht kh). nh lut Henry
CT(kh) + dm <=> dd (*)
qu trnh ha tan cht kh lm gim n nn:
+ Khi P tng => ha tan s tng
+Khi P gim => ha tan s gim
T cn bng (*) thy rng: S tng P s dn n s chuyn dch cn bng sang phi. Nu
tng P ln n ln th ha tan ca cht kh cng tng ln n ln.
nh lut Henry: mt nhit khng i, khi lng cht kh ha tan trong 1 th
tch cht lng xc nh t l thun vi P ca n trn b mt cht lng.
m= k.P
trong : k- h s t l ph thuc vo bn cht ca cht kh, dung mi v
nhit -> gi l h s Henry.
P p sut ring phn ca cht kh trn mt cht lng.
Nu trn mt cht lng c 1 hn hp kh th s ca mi kh t l vi P ring phn ca tng
kh. nh lut Henry ch ng cho cht kh c s nh, P khng ln v kh khng tc dng
ha hc vi dung mi.
IV. Tnh cht ca dung dch.
- Ch xt dung dch: + long
+ cht tan khng bay hi
+ cht tan khng to dung dch rn vi dung mi.
VD: dd mui hoc dd ng khi un ch c H2O bay hi.
Dung dch l tng: l dung dch m ca n tun theo nh lut tng t nh
i vi kh l tng. Cc dung dch rt long c coi nh dung dch l tng.
ca cu t i trong dung dch l tng c tnh theo cng thc ging nh i vi
kh l tng: i ( T ) = i0 + RT ln Ni .
( T ,P)
Tuy nhin v P nh hng rt t n tnh cht ca cht lng nn y i0 v hu

nh ch ph thuc vo T.
dung dch xt y l (rt) long-> coi l dung dch l tng.
1. p sut hi bo ha ca dung dch. nh lut Raun I.
Kho st h 2 cu t: dung mi ch cha 1 cht tan ( cc kt lun rt ra cng ng cho

h nhiu cu t).
K hiu: 2 l cht tan, 1 l dung mi
10
: th ha ca dung mi nguyncht.
i
: th ha ca dung mi trong dung dch.
1 = 10 + RT ln N1
V N1<1 => khi c mt cht tan , ca dungdch s gim i 1 lng l (RTlnNi).

a. p sut hi bo ha ca dung mi nguyn cht ( P10 )
L H(dm) ( vi cht lng L l dung mi nguyn cht)
Hi nm cn bng vi lng gi l hi bo ha, hi bo ha gy P hi bo ha C=12+2=1: p sut hi bo ha ca dung mi nguyn cht ch ph thuc vo nhit . cng
1 nhit , cht no cng d bay hi th P hi bo ha cng ln
Qu trnh bay hi l qu trnh c H > 0 => khi nhit tng th Phi bo ha cng tng.
b. p sut hi bo ha ca dung dch ( P1 )
Ch xt dung dch cha 1cht tan v 1 dung mi: dd (L) <=> H
C=2-2+2 =2
Phi bo ha ca dung dch ph thuc vo c T v C.
iu kin cn bng pha (ca cht lng v hi ca n) t0C, P xc nh l:
ih = il
m ih = i0 h + RT ln Pi (tnh cho 1 mol).
il = i0 l + RT ln N i
ih = il => 0= ioh i0 l + RT ln
R ln
0 l i0 h
Pi
= i
= const
Ni
RT
Ngha l
Pi
= k i = const
Ni
Pi
Ni
t0C xc nh.
=> Pi= ki.Ni
Khi Ni =1 (cht nguyn cht) th ki= Pi0 l p sut hi ca cu t i nguyn cht. T c:

Pi= Pi0.Ni
Kt lun:
- Khi Ni<1 (thm cht tan vo dung dch) => Pi < Pi0: dung dch cha cht tan khng
bay hi th Pp sut hi bo ha ca dung dch lun nh hn Pp sut hi bo ha ca dung mi
nguyn cht cng nhit .
Nu nng dung dch cng ln => Pp sut hi bo ha ca dung dch cng nh.
c. nh lut Rault I
Gi N1 l nng phn mol ca dung dch
P1 v P1,0 ln lt l Pp sut hi bo ha ca dung dch v dung mi nguyn cht cng
mt t0C.
Th: P1 =N1.P1,0
V N1= 1-N2
=>
P1,0 P1
P1,0
n2
P
P
= N 2 =>
= N2 =
P1,0
P1,0
n1 + n 2
Trong : P : gim p sut hi bo ho ca dung dch so vi dung mi.

P
l gim p sut hi bo ho tng i ca dung dch
P1,0
n2: s mol cht ho tan

n1: s mol dung mi.
Nu dung dch long(N1-> 1)=> n1>>n2 th:
P n 2
=> Biu thc ca nh lut Rault I
=
P1,0 n1
Pht biu: gim tng i ca dung dch cha cht ho tan khng bay hi t l vi s
mol cht tan c trong 1 lng dung mi xc nh.
2. Nhit si v nhit ng c ca dung dch. nh lut Rault II
a.Nhit si ca dung dch
* Nhit si ca cht lng: L nhit p sut hi bo ha ca cht lng bng p
sut bn ngoi.
Xt cn bng L H
C=2+2-2 =2
Vy nhit si ca dung dch ngoi s ph thuc vo p sut bn ngai cn ph thuc
vo nng cht ha tan.
- p sut bn ngoi nh nhau, khi dung mi nguyn cht si th dung dch cha cht tan
khng bay hi s cha si v p sut hi bo ha ca dung dch lun lun nh hn p sut
hi bo ha ca dung mi nguyn cht cng 1 nhit . Vy dung dch cha cht tan
khng bay hi c nhit si cao hn dung mi nguyn cht.
- tng nhit si ca dung dch so vi dung mi nguyn cht t s c tnh theo cng
thc Rault 2:
t s = k s = k s
m
M
trong t s =ts,dd-ts,dm (ts,dd: nhit si dung dch, ts,dm: nhit si dung mi nguyn
cht, nng molan; ks: hng s nghim si (ch ph thuc vo bn cht dung mi).
- Khi dung dch si th hi bay ra l ca dung mi nn nng dung dch tng dn, do
nhit si ca dung dch tng dn, nhng khi t n dung dch bo ha th hi dung
mi bay ra lm cho cht ha tan kt tinh li, lc ny nng dung dch khng thay i v
nhit si ca dung dch khng bin i na. Vn dng quy tc pha ta c: C=2-3+2 =1.
Ngha l khi xut hin tinh th cht tan th nhit si ca dung dch ch cn ph thuc
vo p sut bn ngoi.
b. Nhit ng c ca dung dch cha cht tan khng bay hi
Nhit ng c ca cht lng l nhit c cn bng sau: R L
i vi dung dch ta c: C=2+2-2 =2

Vy ng c ca dung dch ngoi s ph thuc vo p sut bn ngai cn ph thuc
vo nng cht ha tan.
Nhit ng c ca dung dch cha cht tan khng bay hi lun thp hn dung mi
nguyn cht. V tun theo nh lut Rault 2:
t d = k d = k d
m
M
trong t s =ts,dd-ts,dm ,ks: hng s nghim ng (ch ph thuc vo bn cht dung mi).
3. S thm thu v p sut thm thu:
a. S thm thu
L s khuch tn mt chiu ca cc phn t dung mi qua mng bn thm (mng bn
thm l mng ch cho cc phn t dung mi i qua m khng cho cc phn t cht ha tan
lt qua). Hin tng ny thy rt r khi hai bn ca mng bn thm cha dung dch c
nng khc nhau hoc 1 bn l dung dch cn bn kia l dung mi nguyn cht; khi
cc phn t dung mi s khuch tn t dung dch long hoc t dung mi nguyn cht
sang pha bn kia nhiu hn s khuch tn theo qu trnh ngc li, do lm tng th
tch ca dung dch pha bn kia.
b. p sut thm thu
Hin tng thm thu lm cho mc dung dch mt pha ca mng bn thm dng ln
cao. Chiu cao ca ct dung dch ny to nn mt p sut lm cho hin tng thm thu
ngng li. p sut c to ra bi ct dung dch ny c trng nh lng cho s thm
thu v c gi l p sut thm thu P. N c tnh theo cng thc:
PV=nRT=
m
RT
M
Trong : V l th tch ca dung dch

n=
m
: s mol cht ha tan.
M
R: Hng s kh l tng.
Chng IX: Dung dch cht in ly

I.Tnh cht ca dung dch in li
1.Cht in ly
L cht khi ha tan trong nc, cc phn t ca n phn ly nhiu hay t thnh cc ion.
Nguyn nhn c bn ca s phn li phn t thnh ion l do tng tc gia cc cht in li
v cc phn t dung mi to thnh cc ion b hidrat ha.
V d: NaCl + mH2O = Na+.nH2O + Cl-(m-n)H2O.
Cc gi tr m, n thng khng xc nh c v ph thuc vo nng v nhit nn
thng c vit:
NaCl + aq = Na+.aq + Cl-.aq
aq: Lng nc khng xc nh
2. Cht in li mnh: L cht khi tan trong nc, tt c cc phn t ca n phn ly thnh
ion.
V d: cht in ly mnh bao gm:
+ cc mui trung tnh: NaCl, NaBr, Na2SO4, NaNO3,...;
+ Cc axit mnh: HCl, HBr, HI, HNO3, H2SO4, HClO4;
+ Cc baz mnh: NaOH, KOH,...
ch s in li mnh, trong phng trnh in li c ghi bng du
V d: NaCl + aq Na+.aq + Cl-.aq
Ngi ta thng vit phng trnh ny mt cch n gin nh sau:
NaCl Na+ + Cl3. Cht in li yu: cc axit hu c HCOOH, CH3COOH, mt s axit v c: H2S,
H2CO3, H2SO3, HClO, HClO2, HClO3, H2SiO3, HF..., cc baz yu v baz t tan: NH3,
Mg(OH)2, Fe(OH)3, cc mui t tan: HgCl2, Hg(CN)2, CdCl2,...
L cht khi ho tan ch c mt phn cc phn t b phn ly thnh ion, trong dung dch
cht in ly yu tn ti cn bng ng gia cc cc ion v cc phn t khng b phn ly.
biu th s in ly khng hon ton, trong phng trnh in ly ca cht in ly yu
dng du
V d: Trong dung dch axit acetic tn ti cn bng
CH3COOH H+ + CH3COO4. Tnh cht bt thng ca dung dch cht in li so vi dung dch cht khng in
li
-
Dung dch cht in li dn in tt, l do trong dung dch c cc phn t mang

in l ion.
Dung dch cht in li c gim p sut hi P' , tng nhit si t ''s ,

gim nhit ng c t' d v p sut thm thu P u ln hn so vi dung dch
cht khng in li cng nng :
P' t ' P'

=
= = i >1
P t P
Tnh cht bt thng ny do cc phn t cht in li phn li thnh cc ion lm s phn

t trong dung dch tng ln. Cc tnh cht trn ca dung dch ph thuc vo nng
cc phn t ny. T c th tnh i bng cch sau:
S phn t c trong dung dch
i = --------------------------------------
S phn t ho tan
S phn t trong dung dch bng s ion c to thnh cng vi s phn t cha b
phn li thnh ion.
II. in ly
nh gi mc in ly ca tng cht a ra khi nim in ly .

1.nh ngha:
S phn t b phn ly
= -------------------------------- (0 < 1)
Tng s phn t b ho tan
- i vi cht in ly yu: <1.
- i vi cht in ly mnh: theo l thuyt => =1 nhng trong thc t o c
bng thc nghim lun <1 (ch dung dch rt long mi c =1). Gi tr o c
bng thc nghim lun <1 c gi l in ly biu kin.
* Gii thch:
- i vi cht in ly yu => s ion c mt trong dung dch t => khong cch gia
cc ion ln => b qua lc tng tc tnh in gia cc ion.
- i vi cht in ly mnh:
+ Trong dung dch long -> khong cch gia cc ion ln => b qua tng tc tnh
in gia cc ion.
+ Trong dung dch c -> s ion c mt trong dung dch nhiu => khong cch
gia cc ion nh =>Khng b qua tng tc tnh in gia cc ion, cc ion ht
hoc y nhau dn n hin tng bao quanh 1 ion c th c nhiu ion tri du to
kh quyn ion => c hin tng nh 1 s phn t khng in ly.
2.Cch xc nh
Gi N l s phn t ho tan, q l s ion m 1 phn t phn ly ra.
S phn t b phn ly l N, do s ion to thnh l .N.q
S phn t cn li khng phn ly l N - .N
S phn t c trong dung dch l N= S ion + s fn t khng phn ly
= q N + (N -N)
q. .N + N - .N
q. - + 1
=> i = -------------------------- = ----------------N
1
i 1
=
q 1
Da vo cng thc ny ta c th tnh c
I c th xc nh bng thc nghim t vic o gim nhit ng c hoc gim
Phi bo ha hoc t t s
'
t s' t d' P
i=
=
=
t s t d P
nhng i o c t vic o t s hoc P cho kt qa km chnh xc so vi vic o t d '

nn thng xc nh i t vic o t d ' : i =
t d'
. Bit i tnh c v ngc li.
t d
V d: Mt dung dch cha 8g NaOH ho tan trong 1000g nc ng c -0,677oC.

Hy xc nh .
Gii:
V q= 2
t
i = ----t = t(dm) - t(dd) = 0- (-0,677) = 0,677oC
t
t = k.C = 1,86.
8
= 0,372 =
40
1,821
= 0,82 hay 82%.
2 1
III. Cn bng trong dung dch cht in ly yu
1. Hng s in ly
Trong dung dch cht in ly yu AB tn ti cn bng sau:
AB
A+ + B-
[A ][. B ]
Hng s in ly ca phn ng K =
+
[AB]
K ph thuc vo bn cht ca cht AB v nhit . i vi mi cht nht nh T=

const th K l hng s. K c trng cho kh nng in ly ca cht in ly yu, K cng ln
th kh nng in ly ca cht in ly cng mnh v ngc li.
2. Mi lin h gia K v . nh lut pha long Ostwald
AB
A+ + BBan u:
C
0
0
Cn bng
C- C
C C
K=
(C)2
C C
K=
2 .C
1
Cng thc ton hc ca nh lut pha long
Ostwald
T cng thc ny nhn thy rng C cng nh th cng ln, c ngha l dung dch
cng long th in ly cng ln.
Khi long 1/C th i vi cht in ly yu nng v cng long th
c th coi qu trnh in ly l hon ton.
C th xc nh c cc C khc nhau nu bit K v ngc li
1/C
Nu < 0,05 th 1- 1 2.C = K
=
K
C
3. Dch chuyn cn bng trong dung dch cht in ly yu

- S in ly ca cht in ly yu l phn ng thun nghch => cn bng trong dung dch
cht in ly yu cng tun theo mi qui lut ca cn bng ho hc.
VD: xt cn bng trong dung dch CH3COOH
CH3COO- + H+
CH3COOH
Nu tng thm nng ca ion axetat bng cch thm mt vi tinh th mui axetat natri
th theo nguyn l dch chuyn cn bng cn bng s dch chuyn t phi sang tri, sao
cho nng ca ion axetat gim i, ngha l lm gim in ly ca axit.
* Kt lun: Khi tng nng ca ion ng loi vi ion ca cht in ly th in ly ca
cht in ly yu gim i.
IV. Thuyt axit- baz ca Bronsted
1.nh ngha axit-baz

Axit l tiu phn (ion hay phn t) c kh nng cho H+ (proton).
Baz l cht c kh nng nhn H+.
V d 1: Trong dung dch HCl
HCl + H2O = Cl- + H3O+ (1)
baz1 axit2
axit1 baz2
ax1 - bz1: HCl/Cl
ax2 - bz2: H3O+/H2O l 2 cp axit baz lin hp

V d 2: Trong dung dch NH3
NH3+ H2O NH4+ + OHbz1 ax2
ax1
bz2
ax1- bz1- NH4+/NH3
ax2- bz2- H2O/OHNhn xt:
- nh ngha axit baz ch c tnh cht tng i: H2O (1) l 1 baz nhng (2)
th H2O li l 1 axit.
- mnh ca 1 cp axit baz ngoi s ph thuc vo bn cht ca cp cn
ph thuc vo mnh ca cp cng tn ti vi n trong dung dch.
- i vi mt cp axit baz lin hp nu axit cng mnh th baz lin hp ca n
cng yu v ngc li.
2. Tch s ion ca nc - ch s hydro (pH)
Nc l cht in ly rt yu, va c tnh axit v va c tnh baz:
H2O + H2O OH- + H3O+
=> K C =
[H O ][OH ]
+
[H 2 O]
V H2O l cht in ly rt yu => [H2O]cb C H O ban u.

=> K C [H 2 O] = [H 3 O ][OH
] = const= K = Tch s ion ca H O.

=> Trong nc nguyn cht : [H O ] = [OH ] = K
+
H2O
H2O
ch ph thuc vo nhit : K H O =10-14 250C.
K H2O
Trong nc nguyn cht(mi trng trung tnh) : [H 3 O + ] = [OH ] = K H O

2
250C [H 3 O + ] = [OH ] = K H O = 10 14 = 10 7 (mol / l)

2
Vy: - Mi trng trung tnh l mi trng trong [H 3 O + ] = [OH ] v 250C
[H O ] = 10
+
M.
Mi trng axit l mi trng trong [H 3 O + ] > [OH ] v 250C [H 3 O + ] > 10 7 M.
Mi trng baz l mi trng trong [H 3 O + ] < [OH ] v 250C [H 3 O + ] < 10 7 M.
3. Hng s in ly axit-baz
a. Hng s in ly ca axit Ka
Trong dung dch ca axit yu HA tn ti cn bng ng sau:
HA + H2O A- + H3O+
[H O ][. A ] =const T= const

=
+
Ka
[HA]
Ka l hng s in ly ca axit trong nc, c trng cho mnh ca axit. Ka cng cao
th axit cng mnh. Ka ph thuc vo bn cht ca axit v ph thuc vo nhit .
- Axit mnh : khng dng Ka v coi 1 .
- Axit yu ( 0 < < 1 ) c hng s cn bng Ka.
b. Hng s in ly ca baz Kb
Trong dung dch ca baz yu B tn ti cn bng ng sau
B + H2O BH+ + OH-
[BH ][. OH ]
K =
+
[B]
Kb l hng s in ly ca baz B, ph thuc vo bn cht ca baz v nhit . T=

const th Kb = const.
4.Mi lin h gia Ka Kb ca 1 cp axit-baz lin hp
Xt mt cp A/B lin hp. Khi ho tan trong nc xy ra qu trnh in ly nh sau:
B + H3O+
Ka
A + H2O
Kb
B + H2O A + OH
[B].[H 3O + ]
Ka =
[A]
[
A].[OH ]
Kb =
[B]
[
B].[H3O+ ] [A].[OH ]
Ka .Kb =
.
= [H3O+ ][. OH ] = KH O =1014 25 C
[A]
[B]
o
Vy i vi 1 cp A-B lin hp th Ka.Kb = [H3O+][OH-] = KH2O = 10-14

Trong 1 cp axit - baz lin hp nu axit cng mnh th baz cng yu v ngc li.
VD: K a ( CH COOH ) = 1,75.10 5
3
K b ( CH COO ) = 10 14 / 1,75.10 5 = 5,71.10 10 > K b ( H2O)

3
CH3COO trong nc th hin tnh baz (yu):

CH3COO- + H2O CH3COOH + OH5. Ch s hydro - pH
pH = -lg[H3O+]
- Mi trng trung tnh [H 3 O + ] = 10 7 M => pH= 7 250C
- Mi trng axit c
- Mi trng baz
[H O ] > 10
[H O ] < 10
+
M => pH <7 250C
M => pH >7 250C
Cch xc nh pH: + Xc nh bng my o pH.

+ S dng giy o pH.
- Cht ch th mu: L cht thay i mu theo gi tr pH. Thng gp cc ch th mu
trong phng th nghim.
+Qu tm.
+Metyl da cam: ch th mi trng axit yu.
+Phenol phatalein: ch th mi trng kim.
Khong chuyn mu: l khong pH trong mu ca ch th bin i c. i

vi ch th mu c 1 khong chuyn mu xc nh.
VD: phenolphtalein: + pH =0 8: khng mu.
+ pH =8-10 : hng
+pH =10-14 thm
Metyl da cam: + pH =0 3: hng
+ pH =3-4,4 : da cam
+ pH =4,4-14 vng.
V. Tnh pH ca cc dung dch axit- baz- mui
1. Tnh pH ca dung dch axit mnh 1 bc

Xt dung dch axit mnh HA, nng Ca, trong dung dch tn ti cc cn bng:
(1)
HA + H2O A- + H3O+
+
2H2O
H3O + OH
(2)
+
Trong dung dch tn ti cc ion H3O , OH , A .
Phng trnh bo ton in tch: [H 3 O + ] = [OH ] + [A ]. Suy ra, ta c h phng trnh
sau
[
[
][ ]
] [ ] [ ] [
H 3 O + . OH = K H2O
H 3 O + = OH + A = OH + C a
] [HK O ] + C [H O ] C [H O ] K
+
=> H3O =
+ 2
H2O
H2O
=0
=> [H 3 O ] =
+
Ca + Ca2 + 4 K H2O
2
Nu dung dch c Ca> 3,16.10-7 (M) (pH<6,5: Ty theo chnh xc yu cu m c cc

iu kin gn ng khc nhau, y chp nhn nu pH<6,5 => mi trng axit): b qua
cn bng (2): tc l b qua [H3O+] do nc phn ly ra so vi [H3O+] do axit phn ly. Do
:
[H3O+]=Ca => pH = -lg Ca
V d: Tnh pH ca dungdch HCl 0,01M. HCl l axit mnh v Ca> 3,16.10-7 (M)
pH =-lg Ca=-lg10-2=2.
2. Tnh pH ca dung dch baz mnh 1 bc
Trong dung dch tn ti cn bng:
BOH = B+ + OHH3O+ + OH2H2O
Nu dung dch khng qu long Cb > 3,17.10-7M th b qua [OH-] do nc in ly.
[OH-] = Cb p(OH) = - lgCb
pH + p(OH) = 14 pH= 14 + lgCb
Nu dung dch qu long Cb < 3,17.10-7M th phi tnh n [OH-] do nc in ly ra,

do gii da vo tnh trung ho v in tch v tch s ion ca nc
][ ]
[ ][ ][ ][
H3O+ . OH = KH2O

OH = H3O+ + Na+ = H3O+ + Cb
O
] KH
[OH ] + C
OH =
OH C b . OH K H2O = 0
Gii phng trnh tm c OH- pH

VD: Tnh pH ca dung dch NaOH 0,01M => pH = 14+ lgCb =14-2=12.
3. Tnh pH ca axit yu 1 bc
Axit HA c nng ban u l Ca
A- + H3O+
(1)
HA + H2O
+
H3O + OH
(2)
2H2O
][
[
]
][ ]
] [ ] [
[ ]
H 3 O + OH = K H 2 O
H 3O + . A
K =
[HA ]
=> ta c h: a
+
= A + OH
H 3O
[HA ] = C A
a
Gii phng trnh bc 3 i vi [H3O+] tm c pH

Tuy nhin khng phi gii phng trnh bc 3 m p dng cc phng php gn ng
vi sai s < 5%
* Nu Ca.Ka 10-12 v 0,1 <
Ca
<100 th c th b qua s in ly ca nc, do
Ka
ch cn xt s in ly ca axit yu
HA + H2O
B Ca
cb Ca- x
Ka =
x2
Ca x
A- + H3O+
0
0
x
x
Gii ra tm c x pH
* Nu Ca.Ka 10-12 v
Ca
> 10 0
Ka
axit rt yu x << Ca c th coi Ca-x Ca
x2
Ka =
Ca
x = Ka .Ca tnh pH
V d: Tnh pH ca dung dch CH3COOH 0,1 M bit Ka = 1,8.10-5

Ca.Ka = 0,1.1,8.10-5 = 10-6 > 10-12
Ca
10 1
=
> 100 [H3O+] < < Ca
5
K a 1,8.10
CH3COOH + H2O
[H O ] =
+
CH3COO- + H3O+
Ka .Ca = 1,8.105.101 pH = lg 1,8.10 6 = 2,87
4. Tnh pH ca baz yu 1 bc
Xt cn bng trong dung dch baz yu B (A l axit lin hp ca B)
B + H2O A + OHH3O+ + OH2H2O
L lun tng t nh trng hp axit yu thy rng tm c [OH ] phi gii
phng bc 3 . i n cc php gn ng:
* Nu Cb.Kb 10-12 v 0,1 <
Cb
< 100
Kb
B + H2O
b Cb
cb Cb-x
A + OH- t [OH-] = x
0
0
x
x
x2
Kb =
Cb x
gii ra tm c [OH-]
* Nu Cb.Kb 10-12 v
C
K
baz yu x<< Cb Cb - x Cb
x = [OH ] = Cb .Kb =
-
> 100
th ch xt phng trnh in ly ca baz yu
Cb .KH2O
Ka
5. Tnh pH ca dung dch mui:

Mui l sn phm ca phn ng trung ho gia 1 axit v 1 baz. Khi ho tan mui
trong nc n phn ly thnh cc ion b hydrat ho. Tu vo bn cht ca cc ion m qu
trnh dng li (pH=7) hoc cc ion tng tc vi nc lm thay i pH ca mi trng,
tc l chng thc hin phn ng thu phn.
nh ngha phn ng thy phn: L phn ng gia cation ca baz yu hoc
anion ca axit yu vi nc lm thay i pH ca mi trng.
V d: Al3+ l cation ca baz yu thc hin phn ng thu phn:
Al2+OH + H3O+
Al3+.H2O + H2O
Al(OH)2+ +H3O+
Al2+OH + H2O
Al(OH)3 + H3O+
Al(OH)2+.H2O + H2O
- c im: - Phn ng thu phn c tnh thun nghch
Nu ion ca axit yu hoc baz c nhiu in tch th s in ly

thnh nhiu nc, nc sau yu hn nc trc. Nu dung dch khng
qu long th cc nc sau c th b qua. Nu dung dch qu long th
phn ng thu phn c th chuyn dch n mc hon ton.
* Cc loi mui c th thu phn:
- Mui to bi anion ca axit yu v cation ca baz mnh (to bi axit yu v baz
mnh), khi ho tan trong nc to thnh mi trng kim. V d: NaCH3COO,
Na2S, Na2CO3, NaClO
NaCH3COO
Na+ + CH3COOCH3COOH + OHCH3COO- + H2O
- Mui to bi anion ca axit mnh vi cation ca baz yu, khi ho tan trong nc
to mi trng axit. V d: NH4Cl, (NH4)2SO4, NH4NO3...
NH4+ + ClNH4Cl
NH4+ + H2O
NH3 + H3O+
- Mui to bi anion ca axit yu v cation ca baz yu, khi ho tan c 2 gc u
thu phn, pH ca mi trng cn ph thuc vo mc thu phn ca c 2 gc.
Nu Ka(cation baz yu) > Kb(anion ca axit yu) th mi trng c pH < 7
Nu Ka(cation baz yu) < Kb(anion ca axit yu) th mi trng c pH > 7
Nu Ka(cation baz yu) = Kb(anion ca axit yu) th mi trng c pH = 7
V d: NH4CH3COO,
NH4CH3COO NH4+ + CH3COONH4+ + H2O
NH3 + H3O+
Ka(NH4+) = 5,6.10-10
Kb(CH3COO-) = 5,7.10-10
CH3COO- + H2O CH3COOH + OHC Ka(NH4+) = Kb(CH3COO-) nn pH = 7
NH4+ + NO2
NH4 NO2
NH4+ + H2O
NH3 + H3O+
Ka(NH4+) = 5,6.10-10
HNO2 + OHKb(NO2-) = 2.10-11
NO2- + H2O
C Ka(NH4+) > Kb(NO2-) nn pH < 7
- Mui to bi axit mnh v baz mnh khng thu phn: NaCl, NaClO4
- Mui axit l cht lng tnh. pH ca mi trng ca dung dch cha n ph thuc
vo mnh ca tnh axit hay tnh baz. V d: Dung dch NaHCO3 l lng tnh v:
H2CO3 + OHKb(HCO3-) = 2,4.10-8
HCO3- + H2O
CO32- + H3O+
Ka2(H2CO3) = 4,8.10-11
HCO3- + H2O
* Tnh pH ca dung dch mui:
Nguyn tc: Ging nh cch tnh pH ca dung dch axit yu hoc baz yu
V d 1: Tnh pH ca dung dch mui MCl3 0,1M. Bit rng ion M3+ c tnh axit, c
hng s in ly Ka = 2.10-3 cc nc thy phn sau c th b qua.
Ka.Ca = 2.10-3.10-1 > 10-12
Ca
0,1
=
< 100 nn b qua [H3O+] do nc in ly
Ka 2.103
M3+.H2O + 2H2O
Ka =
MOH2+ + H3O+
[MOH ][. H O ] = 2.10

[M ]
2+
3+
t x= [H3O+]
x2
Ka =
= 2.103 x pH
0,1 x
V d 2: Cho dung dch K2CO3 0,2M, bit rng Ka2(H2CO3) = 5,6.10-11. Tnh pH ca
dung dch, b qua nc in ly th 2 ca CO32-.
K2CO3
2K+ + CO32HCO3- + OHCO32- + HOH
CO32- l baz lin hp ca HCO3 14
14
Kb(CO32-) = 10 = 10 11 = 1,78 .10 4
Ka.Kb = 10-14
5, 6 . 10
Ka
-4
Kb.Cb = 0,2.1,78.10 > 10
-12
nn b qua s in ly ca nc
Cb
0,2
=
> 100
K b 1,78 .10 4
[ ]
4
4
OH = Kb .Cb = 1,78.10 .0,2 pH= 14+ lg 1,78.10 .0,2 = 11,7
V d 3: Tnh pH ca NH4NO2 10-2 M, bit rng Ka ca NH4 + l 6,3. 10-10 v Kb ca

NO2- l 2.10-11.
V KaC v KbC u ln hn 10-14 rt nhiu nn phn ng ch yu trong dung dch l:
NO2- <=> NH3 +
HNO2
NH4- +
-2
-2
10 M
0
0
Ban u:
10 M
-2
-2
10 -x
x
x
Cn bng:
10 -x
+
Vy [NH4 ]=[NO2 ] v [NH3]=[HNO2]
Ta bit rng K a ca NH4+ l: K a =
1
[NH3 ][ H 3 O + ]
[NH 4+ ]
v K a ca NO2 l: K a
2
[ H O + ][NO2 ]
= 3
[ HNO2 ]
=> K a .K a = [ H3 O + ]2 => [ H3 O + ] = K a . K a
1
=> K a =
2
10 14
= 5.10 4 ; [ H 3 O + ] = 6,3.10 10.5.10 4 = 5,6.10 7 M
11
2.10
=> pH =6,25.
6.Tnh pH ca dung dch axit nhiu bc:
- i vi axit nhiu bc nh H2S, H2SO3, H3PO4 s in ly theo nhiu nc, nc u
tin mnh nht cn cc nc sau yu dn.
V d: Nh s in ly ca axit H2S
HS- + H3O+ Ka1 = 10-7
H2S + H2O
HS- + H2O
S2- + H3O+ Ka2 = 10-13
Do nc 2 yu hn nhiu so vi nc 1 nn c th b qua s in ly ca nc 2 v a v
bi ton tnh pH ca axit 1 bc.
VI. Cn bng trong dung dch cht in ly t tan
1.Tch s ha tan ca cht in ly t tan

Xt dung dch bo ha cht in ly t tan AmBn: Trong dung dch lun tn ti cn bng
gia phn rn khng tan v ion ca n trong dung dch:
mAn+ + nBm- ( thc cht l AmBn (r)
AmBn dd (tan) --> mAn+ + nBm- ).
AmBn (r)
Kc = [An+ ]m[Bm-]n
Trong trng hp ny Kc c trng cho tnh tan ca cht in ly t tan v c gi l tch
s ha tan ca cht in ly t tan Ks.
* nh ngha: Tch s ha tan ca 1 cht in ly t tan l tch s nng ca cc ion trong
dung dch bo ho cht in ly t tan (vi s m l h s tng ng trong phng trnh
in ly).
Ca2+ + SO42- K s ,CaSo = [Ca 2+ ][ SO42 ]
VD:
CaSO4
4
Nh vy Ks l 1 trng hp ca hng s cn bng Kc, bn cht ca Ks l hng s cn bng

K, do mi tnh cht ca K u p dng c i vi Ks.
- Ks ph thuc vo bn cht tng cht v nhit .
2. Mi quan h gia tch s tan Ks v ho tan s
Gi s l nng ca dung dch bo ho, v d i vi dung dch
2Ag+ + SO42Ag2SO4
2s
s
K s,CaSO4 = [Ag + ]2 bh .[SO 4 2 ]bh = (2s)2.s = 4s3 s =
Ks
4
ho tan ca cht in ly t tan s gim i, nu thm vo dung dch mt lng ion

ng loi.
V d: Cho
K s, AgI
= 1,5.10-16 t = 250C. Tnh ho tan ca AgI trong nc
nguyn cht v trong dung dch KI 0,1M.

Gii:
ho tan ca AgI l s
AgI
Ag+ + I- (*)
s
s
[ ] []
Ks,AgI = Ag+ bh. I bh = s2 s = Ks ,AgI = 1,5.1016 = 1,22.108 M

Trong dung dch KI 0,1M KI = K+ + I0,1
0,1
Nng ca ion I- tng ln lm cho cn bng (*) dch chuyn theo chiu nghch lm
cho ho tan ca AgI gim xung. Gi s l ho tan ca AgI trong dung dch KI
Ag+ + Is
s + 0,1
AgI
K s , AgI = [ Ag + ][ I ] = s' (s'+0,1) = 1,5.10 16 V s << 0,1 b qua s so vi 0,1.
Vy s = 1,5.10-15M
s 1,22.108
=
= 8,1.106 ln
ho tan gim i
15
s' 1,5.10
3. iu kin to thnh kt ta v ho tan kt ta
* iu kin to thnh kt ta:
Mun to thnh kt ta cht in ly t tan th tch s nng ca cc ion ca chng
trong dung dch vi s m thch hp phi ln hn tch s ho tan.
V d: Trn 2 th tch bng nhau ca dung dch AgNO3 10-2M vi NaI 2.10-2 M. C
to thnh kt ca AgI hay khng?
[ ]
102
Ag =
= 5.103 M
2
+
[I ] = 2.102
= 102 M
[ ][ ]
3
2
5
16
Vy Ag . I = 5.10 .10 = 5.10 > Ks ,AgI = 1,5.10 vy to thnh kt ta
b. iu kin ho tan kt ta
V d: Ho tan FeS bng dung dch HCl
S2- + Fe2+
(1)
FeS (r)
+
HCl
= H + Cl
(2)
2+
(3)
S + 2H = H2S
2Do (3) nn nng ca ion S gim xung lm [Fe2+].[S2-] < TFeS v lm cho cn
bng dch chuyn theo chiu thun.
Nh vy ho tan mt cht in ly t tan th phi thm vo dung dch mt cht no
c kh nng kt hp vi mt trong cc ion ca cht in ly, lm cho tch s nng
ca cc ion < tch s tan.
Ti liu tham kho:

Chng VII: ng ho hc
Nhit ng ho hc nghin cu phn trc ch mi cho php xt on chiu hng
t din bin ca mt phn ng ho hc v ch kho st h trng thi cn bng, nn
khng h cho bit mt tn hiu no v tc , ngha l s bin i cc tham s ca h theo
thi gian.
V d: Phn ng gia H2(K) + 1/2 O2(K) = H2O(l) c Go298 = -237,2 kJ/mol, Go298 ca
phn ng rt m, c ngha l v mt nhit ng hc phn ng c th xy ra mt cch hon
ton T= 298K v P = 1atm (K= 1041), song thc t cho thy phn ng hu nh khng
xy ra iu kin cho, bi v tc ca phn ng cc k nh, do iu kin
thng ngi ta tng phn ng ny khng xy ra.
ng ho hc l mn khoa hc nghin cu v tc v c ch ca cc qu trnh
ho hc.
I.khi nim v vn tc phn ng
1. nh ngha vn tc phn ng
Vn tc trung bnh ca phn ng: c o bng bin thin nng ca mt
trong cc cht tham gia phn ng hay to thnh sau phn ng trong mt n v thi gian.
Xt phn ng: aA + bB cC + dD
Gi s thi im t1 nng ca cc cht l CA1, CB1, CC1, CD1, thi im t2 th
nng tng ng l CA2, CB2, CC2, CD2. Khi vn tc trung bnh ca phn ng l:
C A 2 C A1
VA,tb =
t 2 t1
Vtb =
, VB,tb =
C B 2 C B1
t 2 t1
, VC,tb =
C C 2 C C1
t 2 t1
, VD,tb =
C D 2 C D1
t 2 t1
C
t
(+)- ng vi cht kho st l sn phm

(-) - ng vi cht kho st l cht tham gia
Vn tc tc thi ca phn ng:
C
dC
=
V = lim
t
dt
t 0
vn tc ca 1 phn ng l n tr:
V =
1 dC A
1 dC B
1 dC C
1 dC D
=
=
=
a dt
b dt
c dt
d dt
2.Cc yu t nh hng ln vn tc
-
Nng cc cht.
Nhit
Cht xc tc.
II. Thuyt va chm hot ng
1.Ni dung:
Gi s xt phn ng A(K) + B(K) AB(K). phn ng xy ra th A v B phi va chm
vi nhau.
C 2 loi va chm:
+ Va chm gy phn ng: gi l va chm c hiu qu(s va chm ny nh).
+ Va chm khng gy phn ng: gi l va chm khng hiu qu(s va chm ny ln).
gy va chm c hiu qu => cc phn t phi c nng lng ln hn nng lng
trung bnh ca h => gi l cc phn t hot ng => vn tc phn ng t l vi tn s va
chm gia cc phn t hot ng.
2.Phn b Boltzman:
C kh l tng A vi tng s mol l N, trong c s phn t hot ng l N* th:
E
A
N*
= e RT => Biu thc nh lut phn b Boltzman.
N
Trong : EA- c gi l nng lng hot ho, n v J.mol-1

R - l hng s kh l tng, R = 8,314 J.K-1.mol-1
III. nh hng ca nng cc cht tham gia phn ng n vn
tc v nh lut tc dng khi lng.
1. nh lut tc dng khi lng

a. i vi h ng th( Cc cht phn ng cng 1 pha).
* nh lut: Vn tc phn ng t l thun vi tch nng cc cht tham gia phn ng
(vi s m thch hp).
V d: aA +bB -> cC (1)
=> gi l phng trnh ng hc ca phn ng.
=> v =k[A]n[B]m
trong [A], [B]: Nng mol/l ca A, B thi im xt.
v : Vn tc tc thi thi im xt.
n,m: Bc phn ng i vi cht A, B -> Xc nh bng thc nghim.
(n+m): Bc chung ca phn ng.
k: H s t l ph thuc vo bn cht ca cht tham gia v nhit.
Vi 1 phn ng c th T =const -> k=const-> gi l hng s vn tc.
Khi [A]=[B]=1mol/l-> v=k -> gi l v ring ca phn ng.
b.i vi phn ng d th: Nu phn ng c cht rn tham gia -> coi nng cht rn =
const v a vo hng s vn tc => cht rn khng c mt trong phng trnh ng hc
ca phn ng.
V d 1: C(gr) + O2(K) CO2(K)
v = k'.const.[O 2 ]n = k[O2 ]n
C. Gii thch: Khi nng tng th vn tc tng: Theo thuyt va chm hat ng: Khi
nng cc cht tham gia phn ng tng th s phn t hot ng c trong 1 n v th
tch tng -> dn n s va chm c hiu qu tng -> vn tc tng.
2.Bc phn ng:

* Bc phn ng c xc nh bng tng s m trong phng trnh ng hc (m+n). Bc
phn ng c th nguyn, hoc l s thp phn hoc bng 0.
- Nu (m+n)=1: phn ng bc 1.
* Cch xc nh bc phn ng:
- Xc nh theo tng cht ri cng li:
Dng phng php c lp: Coi nng cc cht # bng const ( ch c nng cht kho
st bc thay i theo thi gian) bng cch cho nng cc cht ln hn rt nhiu nng
cht xt.
Mt phn ng ha hc l phn ng tng cng ca nhiu giai on trung gian. Mi giai
on trung gian gi l 1 giai on s cp. Vn tc ca giai on s cp no chm cht s
quyt nh vn tc ca c phn ng.
S phn t tham gia vo 1 giai on s cp gi l phn t s ca giai on s cp .
Phn t s ca giai on s cp chm nht xc nh bc chung ca phn ng.
VD: 2HI + H2O2 = 2H2O + I2 (a)
V=k[H2O2]n[HI]m
Phn ng (a) xy ra theo theo 2 giai on s cp:
HI + H2O2 -> HIO + H2O (1) xy ra chm
HIO + HI -> I2 + H2O (2) xy ra nhanh.
giai on (1) quyt nh bc phn ng -> phn t s ca (1) quyt nh bc ca

phn ng (a).
Phng trnh ng hc ca (a) cng l ca (1): v= k[H2O2][HI]
Phn t s ca (1) v (2) u l 1+1=2.
Bc ca p (a) l 1+1=2.
* Ch : nu phn ng n gin ch xy ra theo 1 giai on th n=a, m=b (a, b l cc
h s t lng trong phng trnh phn ng) => Bc phn ng (m+n) =(b+a).
IV. nh hng ca nhit ln vn tc phn ng
1.Quy tc Vant Hoff

Bng thc nghim Vant Hoff cho thy rng nhit c tng thm 10oC th vn tc
ca phn ng tng ln ln, trong khong t 2- 4.
Vt +10
=
Vt
- l h s nhit cho bit vn tc tng ln bao nhiu ln khi nhit tng thm
10 C.
Tng qut:
nhit t1 vn tc ca phn ng l v1, nhit t2 vn tc ca phn ng l v2, ta c:
o
V2 =
t 2 t1
10
V1
l biu thc ton hc ca quy tc Vant Hoff
- Quy tc Vant Hoff ch gn ng trong khong nhit khng cao lm.

2. Phng trnh Arrhenius:
A
A
lnk = + ln => k = .e T
T
Trong : A v l nhng hng s c trng cho phn ng xc nh bng thc

nghim.
* Theo th lnk- 1/A vi tg = A
* Da vo gi tr K hai nhit khc nhau:
A
+ ln
T2
1
1
K2
= A
ln
A
K1
T 2 T1
+ ln
lnK 1 =
T1
lnK 2 =
* Gii thch nh hng ca nhit ti v theo thuyt va chm:

Khi nhit thay i -> c s phn b li nng lng trong h-> s phn t hot ng
thay i -> v thay i.
C th: khi nhit tng vn tc tng do: chuyn ng nhit ca cc phn t tng ln
tn s va chm ca cc cht tham gia tng v khi nhit cao th cc phn t km bn
d phn ng vi nhau.
* ngha ca A trong phng trnh Arrhenius
Xt phn ng: A(k) + B(k) -> AB(k) c bc i vi A v B u bng 1.
(a)
Phng trnh ng hc: =kCA.CB
Ci* = Ci e
Ei
(Ci mol/l ca phn t hat ng i).
RT
Theo thuyt va chm hot ng v ch ph thuc vo Ci*

=> v = C A* C B* = C A e
=> v = C AC B e
( E A + EB )
E Ai
RT
RT
C B e
EA
RT
vi l h s t l.
gi l nng lng hot ha ca phn ng. Ea l nng lng cn thit

t EA + EB = Ea
a mt mol cc cht tham gia phn ng c nng lng trung bnh tr thnh hot
ng.
=> v = C AC B e
Ea
RT
(b)
=> So snh (a) v (b), c: k = e
Ea
RT
=> lnk =
Ea
A
+ ln => lnk = + ln
T
RT
A=-Ea/R
* ngha ca Ea:
hiu r ngha ca Ea ta xt gin nng lng ca phn ng:
I2(K) + H2(K) 2HI(K)
E
K
H2I2
Ea
Ea
Cc cht tham gia c nng lng ng vi mc I, mun phn ng c vi nhau phi

vt qua hng ro th nng c cao l K. Hiu gia mc nng lng K v I chnh l
nng lng hot ho ca phn ng thun Ea. Hiu gia mc nng lng K v II l nng
lng ca phn ng nghch. Hiu gia mc I v II c gi l hiu ng nhit ca phn
ng thun.
Vy nng lng hot ho Ea: Chnh l hng ro th nng m cc cht tham gia phi
vt qua hnh thnh cc sn phm phn ng. Nh vy, nu cc lin kt trong cc cht
tham gia cng bn th nng lng hot ho ca phn ng cng ln.
V.nh hng ca xc tc ln vn tc phn ng
1. nh ngha:
Cht xc tc l cht lm tng vn tc phn ng, nhng n khng b bin i v tiu tn
do phn ng xy ra.
Nu cht xc tc v cc cht tham gia phn ng trong cng mt pha th c gi l xc
tc ng th.
NO
V d:
2SO2(K) + O2(K) 2SO3(K)
Nu cht xc tc khc pha vi cc cht tham gia phn ng th c xc tc d th.
V2O5(r)
V d:
2SO2(K) + O2(K) 2SO3(K)
Xc tc men ng vai tr quan trng i vi qu trnh qu trnh trao i cht: Phn
ln cc phn ng sinh ho xy ra trong c th u di tc dng ca cc enzim
2. c im ca xc tc:
- C tnh chn lc cao: Mt xc tc ch c th c tc dng i vi mt phn ng hay
mt loi phn ng (cho v d)
- Cht xc tc c tc dng lm gim nng lng hot ho ca phn ng
- Cht xc tc lm xc tc cho phn ng thun th cng lm xc tc cho phn ng
nghch, nn cht xc tc lm cho phn ng nhanh chng t ti trng thi cn bng, ch
khng lm chuyn dch cn bng v n lm tng tc phn ng thun v phn ng
nghch vi s ln bng nhau
- i vi xc tc ng th: tc dng ca xc tc t l vi nng ca cht xc tc
3. Gii thch c ch ca xc tc
a. i vi xc tc ng th:
C ch ca xc tc ng th c gii thch bng l thuyt hp cht trung gian.

Xt phn ng: A + B AB xy ra rt chm v c nng lng hot ho Ea rt cao, khi
thm cht xc tc X tc ca phn ng tng ln, c ch ca phn ng nh sau: gm hai
giai on
A + X AX (hp cht trung gian) - giai on ny phn ng xy ra rt nhanh (c
nng lng hot ho thp)
AX + B AB + X - giai on ny xy ra rt nhanh, c nng lng hot ho thp
Nh vy cht xc tc c tc dng a phn ng phi vt qua mt ro th nng cao
thnh phn ng tri qua hai giai on vi ro th nng thp hn.
E
K
AX
Ea
Ea2
A+B
Ea1
AB
II
Tin trnh phn ng
Gi k1, 1, Ea - l hng s tc phn ng, vn tc v nng lng hot ho ca phn

ng khi cha c xc tc
k2, v2, Ea* - khi c xc tc
Ta c:
Ea
+ ln
RT
E *
lnk2 = a + ln
RT
(E E a *)
k
ln 2 = a
k1
RT
lnk1 =
v2 k2
=
=e
v1 k1
Ea Ea *
RT
S ln vn tc tng ln khi c xc tc
b. i vi xc tc d th
C ch ca mt phn ng xc tc d th rt phc tp, cho n nay cha c mt thuyt
duy nht v xc tc d th. Mt phn ng xc tc d th xy ra gm nhiu giai on vt l
v ho hc ni tip nhau
- Giai on u: Xy ra s hp ph ca cc cht tham gia ln cc tm hot tnh ca
cht xc tc
- Giai on 2: Di tc dng ca cc lc ho hc trn b mt xc tc to ra cc hp
cht b mt, dn ti thc hin phn ng trn b mt xc tc
VI. Cc phng trnh ng hc ca phn ng ha hc
Cc phng trnh ng hc m t mi quan h nh lng gia nng ca cc cht phn

ng v thi gian trong cc phn ng bc khc nhau.
1. Phn ng bc mt
Phng trnh phn ng bc 1 c dng:

A -> sn phm.
Phng trnh ng hc vi phn ca phn ng c biu din bng:
v=
d[ A]
d[ A]
= k[ A] hay
= kdt
dt
[ A]
Ly tch phn phng trnh ny s thu c:

ln
[ A]
= kt
[ A]0
y nng [A]0 l nng ban u ca A, [A] l nng ca n thi im t.

Phn ng bc 1 thng l phn ng phn hy ca cc cht. V d:
C2H6 C2H4 + H2
Cc phn ng phn hy phng x cng c xem l cc phn ng bc mt. V d:
232
90
4
Th 228
88 Ra + 2 He
Khi nghin cu cc phn ng bc 1 ngi ta thng ch n mt i lng l thi gian

na phn ng ( cn gi l chu k bn hy i vi phn ng phn hy phng x), k hiu l
t1/2, l thi gian m mt na lng ban u ca cht phn ng b tiu th.
1
2
p dng phng trnh ng hc ca phn ng bc 1 v t1/2 c [A] = [A] 0, ta c:

1
[ A]0
ln 2 0,693
ln 2
= kt1 / 2 => ln 2 = kt1 / 2 hay t1 / 2 =
=
[ A]0
k
k
iu c ngha l thi gian na phn ng ca mt phn ng cho no l mt hng

s c trng cho phn ng . ( mt nhit xc nh).
Chu k bn hy l mt hng s vt l quan trng ca cc cht phng x. N c th dao
ng trong mt khong rng t hng triu nm n my trm nm. V d:
14
C (phng x bta) t1/2 =5,7.103 nm.
8
He (phng x bta) t1/2 = 1,2 giy.
Mt ng dng thc t quan trng ca i lng chu k bn hy l xc nh nin i ca
cc vt c v tui ca cc khong vt. Cng vic ny ngy nay ch yu da trn phng
php o cng phng x 14C..
2. Cc phn ng bc hai
Dng tng qut ca phn ng bc 2 l:
A+ B -> sn phm
Phng trnh ng hc vi phn ca phn ng c biu din bng:
d[ A]
d[ B ]
=
= k[ A][ B]
dt
dt
y chng ta xt trng hp n gin nht l nng ban u ca A v B bng

nhau. V vy c th vit:
d[ A]
d[ A]
d[ A]
= k[ A] 2 hay
= k dt . Ly tch phn 2 v
= k dt
2
dt
[ A]
[ A] 2
=>
1
= kt + const
[ A]
khi t =0 th
1
= const . T :
[ A]0
1
1
1 1
1
= kt k = (
)
[ A] [ A]0
t [ A] [ A]0
Gi t1/2 l thi gian na phn ng. Thay vo phng trnh trn ta c:

t1 / 2 =
1
k[ A]0
Ti liu tham kho:

Chng VIII: cc qu trnh in ho

I.Nguyn tc bin ha nng thnh in nng
1. Phn ng oxy ho kh
V d: Xt phn ng oxy ho kh thng thng xy ra trong dung dch khi nhng thanh
Zn vo dd CuSO4
Zn + CuSO4 = ZnSO4 + Cu
Zn + Cu2+ Zn2+ + Cu
Ho = -230 KJ
2e
Cu2+ trc tip n thanh Zn nhn e
Qu trnh xi ha
Zn-2e =Zn2+
Qu trnh kh
Cu2+ +2e = Cu
c im ca phn ng xi ha kh:
- e trc tip t cht kh sang cht xi ha.
- Nng lng phn ng xi ha kh gii phng di dng nhit.
Trong phn ng oxy ho kh ny cht kh v cht oxy ho c tip xc vi nhau, cc
electron s c chuyn trc tip t cht kh sang cht oxy ho v nng lng ca phn ng
ho hc c to ra di dng nhit. Nhng nu ta thc hin qu trnh oxy ho Zn v qu
trnh kh Cu2+ 2 ni ring bit v cho e chuyn t Zn sang Cu2+ bng 1 dy dn in, c
ngha l to nn mt dng e nht nh th nng lng ca phn ng ny c chuyn thnh
in nng, lm xut hin trong dy dn 1 dng in ngc chiu vi dng electron. cng
l qu trnh xy ra trong mi pin.
2. Nguyn tc bin ha nng thnh in nng
-
Thc hin qu trnh xi ha 1 ni, qu trnh kh mt ni khc.

Cho e chuyn t cht kh sang cht xi ha nh dy dn in th nng lng ca phn
ng ha hc (gii phng di dng nhit) s bin thnh in nng c gi l 1
pin. Pin l 1 dng c thc hin nguyn tc bin ha nng thnh in nng.
3.Cu to hot ng ca pin Cu-Zn
a. Cu to: gm 2 in cc
+ Mt cc l Zn nhng vo dung dch ZnSO4
+ Mt cc l Cu nhng vo dung dch CuSO4
Hai in cc ny c ni vi nhau bng 1 dy dn in. Hai dung dch ZnSO4 v CuSO4
c ni vi nhau bng mt mng ngn.
Thanh Zn c d e ( d tch -) hn thanh Cu => thanh Zn l cc m (-),, thanh Cu l in

cc dng (+).
b. Hot ng
Cc (-):xy ra qu trnh oxy ho: Zn - 2e Zn2+
in cc Zn b n mn dn (in cc mn dn) v Zn2+ tng dn.
Cc (+): xy ra qu trnh kh: Cu2+ + 2e Cu2+ .
in cc Cu dy thm , nng Cu2+ gim
Phn ng tng cng xy ra trong pin: Zn + Cu2+ = Zn2+ + Cu
* K hiu pin:
Vt liu lm Dd nhng
Dd nhng
Vt liu
in cc 1
in cc 1
in cc 2
lm in cc 2
=> s pin Cu-Zn:
(-)Zn | ZnSO4 || CuSO4 | Cu (+)
Khi ni in cc Cu v Zn bng 1 dy dn, cc e s chuyn t cc Zn (-) sang cc (+) do
gia 2 cc c s chnh lch th, lm xut hin mt dng in di chuyn ngc chiu vi
dng electron. Nh vy, to dng in trong pin th gia 2 in cc phi xut hin mt
hiu s in th.
II. Cc loi in cc
1. in cc kim loi:
+
+
+
+
Khi nhng thanh kim loi M vo nc th do tng tc ca

cc phn t nc c cc ->cc ion kim loi b tch ra khi
b mt kim loi i vo dung dch cn cc e li trong thanh
kim loi. Kt qu thanh kim loi s tch in m, cn dung
dch st kim loi s tch in dng, to thnh mt lp in
tch kp.
Trong dung dch tn ti cn bng: M Mn+ + ne
Nu thm mui cha ion Mn+ vo dung dch trn th cn bng chuyn dch theo chiu nghch
v s c mt s ion Mn+ t dung dch chuyn vo thanh kim loi v cn bng trn vn c
thit lp.
Khi cn bng, gia b mt kimloi- dung dch xut hin 1 hiu s in th gi l th
in cc kim loi. Th in cc kim loi ph thuc vo: bn cht cu KL v dung mi, nng
ion kim loi M v nhit .
Nu xt cng 1 nhit , cng 1 dung mi, th in cc kim loi c trng cho bn cht
kim loi: nu th in cc c gi tr cng (-) th kim loi hat ng cng mnh v ngc li.
2. in cc tr nhng trong dung dch cha cp oxy ho kh
-
Cu to in cc tr: Kim loi lm in cc tr v mt ha hc. V d Au, Pt..
- V d: xt in cc oxy ho kh l mt thanh kim loi Pt c nhng vo dung dch

cha cp oxy ho kh FeCl2, FeCl3. Khi Fe3+ s ly e ca thanh Pt v chuyn thnh Fe2+:
Fe3+ + e Fe2+, nn thanh Pt s tch in dng, cn dung dch d Cl- s tch in m. Mt
khc, thanh Pt tch in (+) s ngn cn Fe3+ tip tc ly thm e, nhng li c kh nng nhn
thm e ca FeCl2 bin Fe2+ thnh Fe3+: Fe2+ - e Fe3+. Nh vy: cn bng Fe3+ +e Fe2+
nhanh chng c thit lp, do trn danh gii gia in cc v dung dch s xut hin mt
hiu s in th, c trng cho tnh hot ng ca cp oxy ho kh. Hiu s in th ny ph
thuc vo bn cht ca cp oxy ho kh, nng ca cht oxy ho, cht kh v nhit .
3. in cc kh:
in cc kh l in cc tip xc vi kh v dung dch cha dng xi ha( hoc dng kh)
ca n. iu kin:
1. Kim loi lm in cc tr
2. Khng tc dng ho hc vi kh
3. C kh nng hp ph kh v lm xc tc cho phn ng gia kh v ion ca n
V d: in cc kh H2
c lm bng 1 thanh Pt trn c ph mt lp mui Pt c tc
Pt
dng hp ph kh H2 v c nhng vo dung dch H2SO4
in cc c cn bng sau:
H2
2H3O+ +2e
H2 + 2H2O
Gia in cc v dung dch cng xut hin mt hiu s in

th ph thuc vo nng ca ion H3O+, p sut ca H2 v
H2
nhit .
- in cc H2 chun: V khng th xc nh c gi tr tuyt i ca hiu s in th gia
in cc v dung dch, nn phi quy c ly 1 in cc no lm chun v gn cho n mt
gi tr hiu s in th. Ngi ta quy c ly in cc chun hidro lm chun. l in cc
kh H2 c thm iu kin sau: P H = 1atm v [H3O+]=1M. Trong iu kin nh vy, hiu s
2
in th ca in cc vi dung dch nhit bt k c quy c bng 0,00(V) v c k

hiu l 0
* iu kin chun ca cc loi in cc:
-
Nng cc dng tham gia phn ng in cc bng 1M, nu l cht kh th P= 1atm.

nhit xc nh.
V d in cc kim loi Cu2+ + 2e = Cu [Cu2+] = 1M hay in cc chun ca Cu l

thanh Cu nhng trong dung dch Cu2+ nng 1mol/l.
IV. Sut in ng ca pin
1. nh ngha: Sut in ng (s) ca pin l gi tr hiu s in th ln nht gia 2 in

cc ca pin, c o bng (V), k hiu l E.
E = (+) - (-)
Trong : (+)- in th ca in cc dng
(-)- in th ca in cc m
(Nu theo quy c trn E lun dng, trng hp tng qut E = in th in cc phi in th in cc tri)
2. Cc yu t nh hng n E- Cng thc Nernst
Xt pin: (-) Pt | Sn4+, Sn2+ || Fe3+, Fe2+ | Pt (+)
Cc (-): Xy ra qu trnh xi ha : Sn2+ - 2e = Sn4+
Cc (+): Xy ra qu trnh kh : 2Fe3+ + 2e = Fe2+
Phn ng trong pin l phn ng tng cng 2 qu trnh 2 in cc:
2Fe3+ + Sn2+ 2Fe2+ + Sn4+ (*)
Nu pin lm vic thun nghch nhit ng T, P =const th:
'
G = Wmax
= n.E .F
Trong :
n- l s e trao i gia cht kh v cht oxy ho

F- Hng s Faraday, F = 96.500 C.mol-1
E- Sut in ng ca pin.
G 0
G
0
nu iu kin chun => E =
E=
n.F
nF
Vi phn ng (*) c G T = G T0 + RT ln
[ Sn 4+ ][ Fe 2+ ]2
[ Sn 2+ ][ Fe 3+ ]2
Chia c 2 v cho 2F c:
G T
G o T RT [ Sn 4+ ][ Fe 2+ ]2
=
ln
2.F
2F
2F [ Sn 2+ ][ Fe 3+ ]2
[
[
][
][
RT Sn 2 + Fe 3+
E=E +
ln
2F
Sn 4 + Fe 2+
o
]
]
2
2
Tng qut: Phn ng xy ra trong pin l:

aA + bB <=> cD +dD ( A, B, C, D l cht tan trong dung dch)
C E = E 0 +
RT [ A]a [ B ]b
ln
nF [C]c [ D]d
-> Cng thc Nernst biu th E =f(C,T).
cc yu t nh hng n E l: Nng v nhit .

T = 298K, thay R = 8,314 J.K-1.mol-1, F = 96.484 C.mol-1 v i sang logarit thp phn.
E = E0 +
0.059 [ A]a [ B ]b
lg
n
[C]c [ D]d
V. Th in cc (th kh)
1. Cp xi ha kh:
V d: Trong dung dch tn ti Cu2+ nhng trong phn ng th Cu2+ + 2e = Cu
gi Cu2+/Cu l 1 cp xi ha kh.
* nh ngha: Cp xi ha kh l mt cp gm cht xi ha v cht kh, chng c th bin
i ln ra nhau trong qu trnh phn ng.
- K hiu cp xi ha kh l cht xi ha/cht kh hoc cht xi ha, cht kh.
- Vi cch quy c ny phn ng in cc bao gi cng l qu trnh kh
xi ha + ne = Kh
- Cp xi ha kh chun: L cp xi ha kh khi [xi ha] =[kh] = 1M ( nu l cht kh P=
1atm).
2. Th kh
Quy c qu trnh in cc l qu trnh kh dng: Oxh + ne -> Kh
Th o c gi l th kh ca cp oxiha kh. K hiu l ox
Kh
* Th kh l i lng c trng cho kh nng xi ha kh ca cp xi ha kh

- Nu ox c gi tr cng ln (cng dng) -> dng oxi ha hot ng mnh, dng kh
Kh
yu.
Nu ox
c gi tr cng nh (cng m) -> dng kh hot ng mnh, dng xi ha

Kh
yu.
Th kh ca 1 cp oxiha kh chun gi l th kh chun 0 ox Kh
* Cch xc nh th kh chun ca mt cp oxiha kh:
Vic xc nh gi tr tuyt i th kh ca cc in cc l khng th lm c, nhng nu
quy c th kh ca mt in cc no lm chun v bng cch so snh s xc nh c
th kh ca cc in cc khc
- Quy c: Chn in cc kh hydro lm in cc so snh vi [H 3 O + ] = 1M, PH = 1atm v
2
gn cho n gi tr in th = 0 mi nhit , k hiu

th ny tng ng vi cn bng in cc: 2H3O+ + 2e
oH3O+/H2 = 0,00 (V). Hiu s in

H2 + 2H2O
xc nh th kh ca mt in cc ngi ta ghp in cc ny vi in cc chun

H2 thnh mt pin, ri xc nh sut in ng ca pin to thnh. Gi tr sut in ng
ca pin chnh l th in cc chun ca in cc cn xc nh in th. N c gi tr
dng nu th ca in cc xc nh cao hn th ca in cc chun H2 v ngc li.
VD: Pt, H2(1atm) || Cu2+ | Cu
0
o c E0= 0,34 (V) = Cu
-0=0,34 (V). (v Cu l in cc dng ca pin)
2+
Cu
Bng phng php ny ngi ta xc nh c th kh chun ca nhiu cht v lp

thnh bng th kh chun.
-
Vi cc nguyn t c nhiu mc xi ha khc nhau-> tnh 0 ca 1 cp da vo

0 ca cc cp khc bng cch lp chu k kh kn:
0
Fe
VD: Fe3+ + 1e Fe2+ ,

Fe2+ + 2e Fe
0
Fe
Fe3+ + 3e Fe
= 0,77( V ) = 10
3+
Fe 2 +
= 0,44( V ) = 20
2+
Fe
=?
0
Fe 3 +
Fe
tnh 0 ,lp chu trnh kh kn:

+ne
S xi ha (+) cao nht
S xi ha (+) thp nht
G 0
G10 +n1e
G 20
+n2e
S xi ha (+) trung gian

G = G + G
0
0
1
( G = nE 0 F = n 0 F )
0
0
2
=> n 0 F = n1 10 F n 2 20 F
=> 0 =
n1 10 + n 2 20
n
C th v d trn:
G 0
3+
Fe
G10
+3e
+1e
Fe
+2e G 0
2
Fe2+
G 0 = G10 + G 20
=>
0 =
1 10 + 2 20 0,77 + 2(0,44)
=
= 0,036(v)
3
3
3. Cc yu t nh hng n th in cc
T v d trn vi phn ng: 2Fe3+ + Sn2+ 2Fe2+ + Sn4+
[
[
][
][
RT Sn 2 + Fe 3+
ln
C E = E +
2F
Sn 4 + Fe 2+
o
]
]
2
2
M E = + v E 0 = 0 + 0 nn c:
+ = 0+ 0 +
=> + =
= 0
[
[
Fe 3+
RT
(ln
2F
Fe 2+
[
[
RT [Sn
+
ln
2F [Sn
]
]
]
]
RT
Fe 3+
+
ln
2F
Fe 2+
4+
2+
]
]
[Sn ])
[Sn ]
4+
- ln
2+
2
2
Tng qut:
C phn ng in cc: axh + ne bKh
=> i = 0 i +
RT [Oxh]
ln
nF
[Kh]b
25 C: i =
0
0,059 [Oxh]
+
lg
n
[Kh]b
* i vi in cc kim loi: Mn+ + ne M

0,059
=0 +
lg[M n+ ]
n
* i vi in cc kh: v d : O2(k) + 4 e + 4 H+ 2H2O
=0 +
0,059
lg([H + ]4 . pO2 )
4
* i vi in cc tr trong dung dch xi ha kh: Nu trong phn ng kh c mt H+, OH=> pH thay i => pH lm thay i th kh.
VD1: Sn2+
+ 2e Sn4+
=0 +
[
[
0,059 Sn 4+
lg
2
Sn 2+
]
]
VD2: MnO4- + 5e + 8H+ Mn2+ + 4 H2O
0,059 [ MnO4 ][ H + ]8
= 0 +
lg
5
[ Mn 2 + ]
V. Chiu v trng thi cn bng ca phn ng xi ha kh xy ra

trong dung dch nc.
1. Chiu ca phn ng oxy ho kh:

i vi phn ng oxy ho kh da vo mi lin h gia G v E xt chiu, bit rng
G = -n.E.F. phn ng xy ra th G < 0 hay -n.E.F <0 E > 0 m i vi phn ng oxy
ho kh th E = ox - kh ox > kh
Trong : ox - Th kh ca cp oxy ho kh c dng oxy ho tham gia phn ng
kh - th kh ca cp c dng kh tham gia phn ng
Quy tc v chiu ca phn ng oxy ho kh:
C 2 cp oxy ho kh ox1/kh1 v ox2/kh2, nu
ox / kh >ox / kh
1
th phn ng xy ra theo
chiu: ox1 + kh2 ox2 + kh1.

iu kin chun: Go = - n.Eo.F < 0 Eo >0 oox > okh
Ch :
Trong trng hp tng qut xt chiu ca phn ng oxy ho kh th phi tnh th
kh ca cc cp oxy ho kh trong iu kin phn ng ri mi so snh v rt ra kt
lun
Theo cng thc Nernest th kh ca mt cp oxy ho kh ph thuc vo nng cc
dng oxy ho, dng kh, ph thuc vo nhit v pH ca mi trng, nn khi
thay i mt cc thng s trn th th kh ca cc cp s thay i v c th dn n
lm thay i chiu ca phn ng oxy ho kh.
Di y xt mt vi v d v chiu ca phn ng oxy ho kh.
V d 1: Cho bit cn bng sau 25oC trong dung dch nc:
2Cr2+ + Cd2+
2Cr3+ + Cd, bit o Cr
3+
/Cr 2 +
= 0,41V , o Cd 2 + /Cd = 0,4V
a. iu kin chun phn ng xy ra theo chiu no ?

b. Trn 25 ml dung dch Cr(NO3)3 0,4M vi 50 ml dung dch Cr(NO3)2 0,02M, 25 ml
dung dch Cd(NO3)2 0,04M v bt Cd. Hi chiu phn ng iu kin ny ?
Gii:
a. oox = o Cd2 + /Cd = 0,4V ; okh = o Cr
3+
/Cr 2 +
= 0,41V
oox > okh, vy iu kin chun phn ng xy ra theo chiu thun

b. Tnh nng ca cc dng oxy ho v dng kh
[Cr ] = 0,4.00,1,025 = 0,1M ; [Cr ] = 0,020.,10,05 = 0,01M ; [Cd ] = 0,040.0,1,025 = 0,01M

3+
Cr 3 + /Cr 2 + = o Cr 3 + /Cr 2 + +
2+
[
[
2+
]
]
0,059 Cr 3+
0,1
lg
= 0,41 + 0,059lg
= 0,351V
2+
1
0,01
Cr
0,059
0,059
lg0,01 = 0,459V
lg Cd 2 + = 0,4 +
2
2
Cd 2 + /Cd = o Cd 2 + /Cd +
ox = Cr 3 + /Cr 2 + = 0,351V ; kh = Cd 2 + /Cd = 0,459V , vy iu kin ny phn ng xy ra
theo chiu nghch.

V d 2:
nh hng ca nng ca dng oxy ho v dng kh ln chiu ca phn ng oxy ho
kh
Cu2+ + e Cu+ ;
o Cu2+/Cu+ = 0,153V
Sn4+ + 2e Sn2+;
o Sn4+ /Sn2+ = 0,15V
iu kin chun do
oCu2+/Cu+ > oSn /Sn

4+
2+
nn phn ng xy ra theo chiu Cu2+ + Sn2+
Cu+ + Sn4+
Nu tng nng ca [Sn 4 + ] hoc [Cu + ] th:
Sn4+ /Sn2+ =
4+
2+
Sn /Sn
Cu2+ /Cu+ = o Cu2+ /Cu+

n khi
[ ]
[ ]
[Cu ]
+ 0,059lg
[Cu ]
0,059 Sn4+
+
lg 2+
2
Sn
2+
+
Sn4+/Sn2+ > Cu2+/Cu+

o
hay
oSn4+/Sn2+ > Cu2+/Cu+
th phn ng s xy ra theo chiu
nghch.
2. Trng thi cn bng ca phn ng oxy ho kh
Phn ng oxy ho kh t n trng bng khi GT = n.ET .F = 0 ET = 0 hay ox = kh.
Hng s cn bng ca phn ng xi ha kh:
G 0 = RT ln K
mt khc G 0 = nFE 0
=> RT ln K = nFE 0
lnK =
n.E o .F
(phn ng trong dung dch th K=Kp=KC).
RT
n.E o
T = 298K lgK =
0,059
Trong o: n- l s e trao i gia dng oxy ho v dng kh

Eo = oox- okh
V d: Tnh hng s cn bng K ca phn ng sau:
2Fe3+ + Sn2+
2Fe2+ + Sn4+ ;
o Fe3+ /Fe2 + = 0,77V ; o Sn
4+
/Sn 2 +
= 0,15V
oox = oFe3+/Fe2+ ; okh =oSn4+/Sn2+

lg K =
2.(0,77 0,15)
= 21 K= 1021
0,059
VI. Qu trnh in phn
1. nh ngha:
in phn l qu trnh oxy ho v qu trnh kh xy ra trn b mt in cc khi cho dng
in mt chiu i qu dung dch cht in ly hoc cht in ly nng chy.
V d: in phn dung dch CuCl2
Khi cho dng in mt chiu i qua dung dch CuCl2 th di tc dng ca in trng
cc cation Cu2+ i v cc m, cn anion Cl- i v cc dng. Ti cc in cc s xy ra hin
tng phng in.
Catt (-): Cu2+ + 2e Cu
Ant (+): 2Cl- -2e Cl2
Cu2+ + 2Cl- Cu+ Cl2
y chnh l phn ng oxy ho kh xy ra khi in phn dung dch CuCl2. Phn ng ny
khng t xy ra c, m n ch xy ra c di tc ng ca ngun in mt chiu bn
ngoi. Do qu trnh in phn l qu trnh bin i in nng thnh ho nng.
2. S phn cc:
Khi in phn trng thi in ca in cc (th v mt in tch ca lp in tch kp)
b thay i. Th ca in cc s khc vi th ca n lc cn bng (khi cha c dng in).
Hin tng ny c gi l s phn cc.
Tu thuc vo tnh cht ca qu trnh lm thay i th ca in cc c 3 loi phn cc
khc nhau:
a. S phn cc v nng :
Khi in phn nng ca cc ion catt v ant b thay i. ant do kim loi b ho
tan, nng ca ion tng ln, cn catt xy ra s kh nn nng ca ion gim i, dn
n th ca in cc gim. Nu mt dng in cng ln th s bin i nng ca cc
ion cng ln, do s phn cc cng ln. Cn khuy mnh gim s phn cc.
b. S phn cc ho hc:
Khi in phn cc sn phm thot ra cc in cc dn ti s to thnh 1 pin c chiu
ngc vi chiu dng in
c. S phn cc in ho:
Khi nhng 2 in cc vo dung dch cht in ly v ni 2 in cc vi ngun in mt

chiu th cc e s di ant (+) ti catt (-) nhng cc e khng t i qua dung dch c,
nn nu trn cc in cc khng xy ra cc qu trnh in ho th mt in cc s tch in () do tha e, cn in cc kia tch in (+) lm cho cc lp in tch kp cc in cc b
thay i, do gia 2 in cc s xut hin mt hiu s in th c chiu ngc vi chiu
ngun in bn ngoi.
V d: in phn dung dch CuCl2
(+) Ant:
(-) Catt:
2Cl- -2e Cl2
Cu2+ +2e Cu
Cu2+/Cu
Xut hin Cl2/ClSn phm thot ra cc in cc dn ti s to thnh mt pin Epin = th phn cc = Efc.
3. Th phn hu:
S in phn ch xy ra mt in p hon ton xc nh. in p ti thiu gia 2 in
cc s in phn bt u xy ra c gi l th phn hu.
Nh vy, v mt l thuyt th Efh = sut in ng ca pin to bi cc sn phm thot ra
ant v catt = Efc, nhng thc t Efh > Efc v Efh = Efc + = Efh - Efc, c gi l qu
th. ph thuc vo bn cht ca in cc, trng thi b mt in cc, thnh phn dung
dch, mt dng, ...
4. S in phn cht in ly nng chy
Khi cho dng in mt chiu i qua cht in ly nng chy th cc cation i v catt (-),
cn cc anion i v ant v xy ra hin tng phng in.
V d: in phn nng chy NaCl
(-): Na+
(+): ClNa+ + e Na
Cl- -e 1/2Cl2
NaCl Na + 1/2 Cl2

5. in phn dung dch cc cht in ly:
Trong dung dch ngoi cc ion do cht in ly phn ly ra cn c ion H3O+ v OH- do nc
in ly ra. Khi cho dng in mt chiu i qua dung dch cc cation kim loi Mn+ v ion
H3O+ s i v catt cn cc anion gc axit v ion OH- s i v ant (-).
a. Qu trnh catt:
Xy ra phn ng kh cc cation Mn+ theo phn ng: Mn+ + ne M (1) hoc ion H3O+
theo phn ng 2H3O+ + 2e H2 + 2H2O (2) tu thuc vo kh nng oxy ho ca chng c
nh gi bng th kh. Trong dung dch c pH = 7 th kh ca hydro l :
H O + /H = 0,059.pH = 0,413V . V pH =7 phng trnh (2) c vit di dng 2H2O

3
2
+ 2e -> H2 + 2OH-
Cc kim loi c th kh Mn+ /M > H3O+ /H2 = 0,413V th b kh catt theo (1).
Theo bng dy th in cc tiu chun l nhng kim loi ng sau st, nhng do
qu th ca hydro nn b y n cc kim loi ng sau Al (khng k Al) b kh
catt.
Trng hp ngc li: Cc ion kim loi t Al tr v trc dy th kh s khng b
kh m ion H3O+ s b kh theo phng trnh (2).
b. Qu trnh ant:
Xy ra s oxy ho hoc anion, hoc ion OH- hoc cht lm in cc tu thuc vo kh
nng kh ca chng.
Nu l in cc kim loi: Do kim loi c kh nng kh mnh cht nn ant s b tan
ra thao phn ng: M- ne Mn+
Nu ant l in cc tr: Xy ra qu trnh oxi ho anion gc axit hoc ion OH- tu
theo kh nng kh ca chng gim dn theo dy sau: S2- > I- >Br- > Cl- > F- > OH- >
anion cha oxy.
V d 1: Vit s in phn dung dch Na2SO4 dng graphit lm in cc( ant tr).
Na2SO4
Catt
2Na+ + SO42-
H2O , 2Na+
2H2O + 2e = H2 + 2OH-
Ant
SO42- ,H2O
3H2O - 2e = 2H3O+ + 1/2 O2
T s inphn trn ta thy thc cht l s in phn nc. Vai tr ca Na2SO4 y ch

l cht dn in.
V d 2: Vit s in phn dung dch CuSO4 dng ant bng ng.
CuSO4
Catt
H2O , Cu2+
Cu2+ + SO42-
Cu2+ + 2e = Cu
Cu to thnh bm vo catt
Ant (Cu)
SO42- ,H2O
Cu - 2e = Cu2+
Ant tan dn
Ti liu tham kho:


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WWW.DAYKEMQUYNHON.

- Kch thc khong 1 A ( 10-10 m).

Trong h = 6,626 .10-34 J.s - hng s Planck

Khi e chuyn t qu o ny sang qu o khc th xy ra s hp th hoc gii phng

- Khng gii thch c s tch cc vch quang ph di tc dng ca in trng, t

1. Lng tnh sng ht ca cc ht vi m

Trong : m - Khi lng ca ht, kg

i vi ht v m: m kh ln (h =const) kh nh -> tnh cht sng c th b

i vi ht vi m : m nh (h =const) kh kh ln -> khng th b qua tnh cht

ca ht v cng nh nn b qua tnh cht sng ca ht.

vx- bt nh (sai s) v vn tc theo phng x

2dv m t xc sut tm thy electron thi im t trong yu t th tch dv bao

dv = 1 L iu kin chun ha hm sng.

2. Phng trnh Schrodinger:

3. Obitan nguyn t v my electron.

Mi gi tr nghim gi l 1 obitan nguyn t, k hiu l AO.

IV. H 1 e ( nguyn t H v ion tng t).

1. Phng trnh sng:

Trong r: khong cch gia ht nhn v e.

th nng V ch thuc vo r => trng to ra l trng xuyn tm ( trng c i

gii phng trnh sng trn a v h ta cu: (x,y,z) (r,,)

n: c gi tr nguyn dng, gi l s lng t chnh.

(r,,)= Rn,l (r).Ym,l(,)

- L hm xuyn tm ph thuc vo hai tham s n, l

Y (,) - L hm gc ph thuc vo hai tham s l l, m.

Nh vy hm sng thu c ph thuc vo 3 s lng t l n,l,m : n,l,m hay ni

cch khc: Mt hm sng (1AO) c c trng bng 3 s lng t n,l,m.

n =2, l =0 => 200=1AO.

n 1 => c ns = AO ns => my ns.

m=1 (x) -> np = AO npx=> my npx

m=-1 (y) -> np = AO npy => my npy.

ns c tnh cht i xng cu, khng ph thuc vo , .

My s: Mt my e phn b ng hng v l 1 khi cu.

Mi hm ns l 2 mt cu i xng nhau qua gc ta c phn (+) v phn (-) theo

5. Chuyn ng ring ca e trong nguyn t:

Chuyn ng xung quanh nhn ( chuyn ng obitan) c c trng bng 3 s

H nhiu e -> e kho st chu tc dng ca:

l c trng cho lc y ca cc e cn li, l cng ln En,l cng ln.

n cng ln th lp electron cng xa nhn v electron c nng lng cng cao.

Lp L ng vi n=2 gm c hai phn lp c c trng

Lp M ng vi n=3 gm c 3 phn lp c c trng l = 1 3p

i vi nguyn t H hay ion 1 e, n xc nh mc nng lng ca e trong nguyn t

i vi nguyn t nhiu e -> Ee =f(n,l) n ch xc nh mc nng lng trung bnh

1. Nguyn l ngoi tr Pauli

VD: Lp K; n=1 => l=0 => m=0=> ms =+ v ms =-

lp K c nhiu nht 2 e: e th nht c ga tr n =1, l=0, m =0 v ms =+ ; e th 2

H qu: Da vo nguyn l pauli c th tnh c s electron ti a trong mt lng

a. Cu hnh dng ch:

* Ch : Trong mt s nguyn t, vit cu hnh e theo nguyn l vng bn trng thi

Nm 1869, Mendeleep khm ph ra nh lut tun han : Tnh cht ca cc

Ngy nay, di nh sng ca thuyt cu to nguyn t, nh lut tun hon v HTTH l

Gm 7 hng ngang ng vi 7 chu k, khng phn bit chu k ln nh, chn l:

c hai phn lp ngoi cng l (n-1)d3ns2

c hai phn lp ngoi cng l (n-1)d4ns2 (n-1)d5ns1

III. S bin i tun hon 1 s tnh cht ca cc nguyn t

A: H s chn tng cng ca cc e cn li i vi e xt.

khi Z tng th EAO gim.

b. Trong 1 nhm: t trn xung trong 1 nhm th:

EAO ha tr tng dn do:

- Hiu E = E np E ns gim do n tng nhanh.

I1 > 0, I1- l nng lng ion ho th nht

Nng lng ion ho th hai ng vi qu trnh bt electront h hai

c. Cc yu t nh hng n nng lng ion ho:

Trong : E l nng lng ca electron xa v cng = 0