Bai Giang Dai Cuong

CHNG 1
MT S KHAI NIM C BAN CUA HOA

HOC
1. Hoa hoc la khoa hoc nghin cu s phu thuc cua tnh
cht cac cht vao thanh phn va cu tao cua chung va
nhng qua trnh lin quan n s bin i cac cht.
Cac cht cu tao t nguyn t va phn t. Cac nguyn
t co th kt hp vi nhau tao thanh phn t nh cac mi
lin kt hoa hoc. Phan ng hoa hoc la qua trnh bin i
cac cht nay thanh cac cht khac.
Nguyn t hoa hoc la tp hp cac nguyn t co cung
in tch hat nhn.
2. Mol: la lng cht co cha s phn t, s nguyn t,
s ion, s electron... hay noi chung la s n v cu truc
(hat) bng s nguyn t
12
C co trong 12 gam ng v cacbon -
12, tc la bng s Avogadro (N
o
= 6,0229.10
23
).
3. ng lng
3a. ng lng cua mt nguyn t
ng lng cua mt nguyn t la lng nguyn t
o co th kt hp hoc thay th mt mol nguyn t
hydro trong phan ng hoa hoc.
ng lng khi cua mt nguyn t (ky hiu: ) la
khi lng tnh ra gam cua mt ng lng cua
nguyn t o.
Cng thc:
n
A

Khi lng mol nguyn t (A) va
hoa tr (n)
. V du Fe co A = 55,84 ng vi 3 trang thai hoa tr: 2, 3, 6 co
3 tr s ng lng la 27,92; 18,61 va 9,31.
3b. ng lng cua mt hp cht
ng lng cua mt hp cht la lng cht o
tng tac va u vi mt ng lng cua hydro hay
cua mt cht bt ky khac.
ng lng khi cua mt hp cht la khi lng
ng lng cua hp cht o tnh ra gam.
Cng thc:
n
M

. Trong o n co y ngha khac nhau tuy
tng loai phan ng.
- Vi cac phan ng trao i, n la tng s n v in tch
(tnh ra n v e) ma phn t hp cht trao i vi cac
phn t khac.
- Vi phan ng trung hoa: n la s H
+
cua phn t axit (la s
H
+
cua phn t baz) tham gia phan ng.
1
- Vi phan ng oxy hoa - kh, n c tnh bng s
electron ma mt phn t cht o trao i vi cht khac.
3c. nh lut ng lng
Cac cht tng tac hay thay th nhau theo nhng lng
ty l vi ng lng cua chung.
Cng thc: khi m
A
gam cht A tng tac vi m
B
gam cht
B th ta co:
B
A
B
A
m
m
CU HOI VA BAI TP CHNG 1

Cu 1. Mol la g? Tnh khi lng (ra g) cua mt mol phn t
clo va mt mol nguyn t clo
Cu 2. ng lng la g? Th nao la ng lng khi
cua mt nguyn t va mt hp cht?
Cu 3. Vit cng thc tnh ng lng khi cua n cht
t khi lng nguyn t va cng thc tnh ng lng
khi cua axit, baz, mui t khi lng phn t.
Cu 4. Phat biu nh lut ng lng. Vit cng thc
toan hoc cua nh lut ng lng
Cu 5. Vit cac phng trnh phan ng gia H
3
PO
4
va Ba(OH)
2
.
Tnh ng lng cua mi cht trong cac phan ng. Cho H
= 1, P = 31, O =16, Ba = 127.
Cu 6. Cho phan ng: Al
2
(SO
4
)
3
+ 6NaOH = 2Al(OH)
3
+
3Na
2
SO
4
. Tnh ng lng khi cua Al
2
(SO
4
)
3
. Cho Al = 27, S =
32, O =16.
Cu 7. Oxy hoa hoan toan 0,235g nguyn t M thu c 0,40g
xt MO. Hay tnh ng lng cua M, bit ng lng
cua oxy bng 8.
Cu 8. Tnh ng lng cua Fe trong phan ng hoa tan Fe
vao dung dch HCl va phan ng hoa tan Fe vao dung dch HNO
3
(tao ra kh NO). Tnh ng lng cua axit trong mi phan
ng o.
Cu 9. Vit phng trnh phan ng hoa tan FeO trong dung
dch HNO
3
(tao thanh NO). Tnh ng lng cua mi cht
trong cac phan ng.
Cu 10. Mt hp kim A cu tao t kim loai R va magi,
thanh phn khi lng mi kim loai la 50%. Hoa tan 7,2 gam
A vao dung dch HNO
3
th co 4,032 lt kh NO bay ra (ktc). Tnh
ng lng cua R.

===========================
2
CHNG 1:
CU TAO NGUYN T VA
H THNG TUN HOAN CAC
NGUYN T HOA HOC
1.1. CAC HAT C BAN TAO THANH NGUYN T
Electron (e) co khi lng bng 1/1837 .v.C hay
9,1095.10
-28
g va mang in tch -e (bng -1,6021.10
-19
culng).
Proton (p): mang in tch dng + e, co khi lng
bng 1,00728 .v.C hay 1,672.10
-24
g.
Ntron (n): khng mang in tch, co khi lng bng
1,00867 .v.C hay 1,675.10
-24
g.
1.2. M HNH NGUYN T CO HAT NHN
Mi nguyn t co mt hat nhn mang in tch dng
va cac electron quay chung quanh. Kch thc nguyn t vao
c 10
-10
m. V khi lng electron rt nho nn hu ht khi
lng nguyn t tp trung hat nhn.
Hat nhn cu tao t cac hat p va n (c bit hat
nhn nguyn t H ch cu tao t mt hat p) va co ng
knh c 10
-15
m 10
-14
m. Trong hat nhn, cac hat p va n lin
kt vi nhau bng mt loai lc c bit goi la lc hat
nhn. in tch hat nhn (Z) bng s p co trong hat nhn.
in tch hat nhn (Z) (khi tnh ra n v e) c xac
nh bng thc nghim theo cng thc Moseley:
) b Z ( a
.
Trong o: la tn s quang ph tia Roenghent phat ra bi
nguyn t o khi b kch thch, a va b la cac hng s c
trng cho vach quang ph tng ng.
M hnh nguyn t Bohr
Khi ap dung quan nim lng t nng lng xem xet
cu tao quang ph vach cua nguyn t hidro, nha bac hoc
an Mach N.Bohr a xut m hnh nguyn t vi ni dung
chnh nh sau:
1. Trong nguyn t, electron ch co th chuyn ng trn
nhng quy ao xac nh co ban knh xac nh. Khi quay trn
cac quy ao o nng lng cua electron c bao toan.
2. Mi quy ao ng vi 1 mc nng lng cua electron.
Quy ao gn nhn nht ng vi mc nng lng thp
nht. Quy ao cang xa nhn ng vi mc nng lng cang
cao. Nng lng cua electron khi quay trn quy ao trong
nguyn t hidro c tnh bng cng thc:
2 2
4
2
0
n
n
1
.
h
me
.
8
1
E

3
Trong o:
0
la hng s in mi cua chn khng, m la khi

lng va e la in tch cua in t, h la hng s Plank; n
co th ly cac gia tr nguyn dng: 1, 2, 3 ...
3. Khi electron chuyn t quy ao nay sang quy ao khac
th xay ra s hp thu hoc giai phong nng lng. Lng
t nng lng cua bc xa c giai phong hoc hp thu
bng hiu gia hai mc nng lng va co tn s (va
bc song ) c xac nh bng cng thc (khi electron
chuyn t mc n n mc n): = h = h
c
= E
n
- E
n

Thuyt Bohr cho phep giai thch c quang ph, cu tao
quang ph vach cua nguyn t hidro va nhng nguyn t
ging hidro. No cung cho phep tnh c ban knh nguyn t
hidro trang thai c ban: a = 0,529.10
- 10
m = 0,529 (a c
goi la ban knh nguyn t Bohr). Tuy nhin thuyt Bohr khng
giai thch c cu tao quang ph cua cac nguyn t phc
tap cung nh s tach cac vach quang ph di tac dung
cua in, t trng.
1.3. C HOC LNG T
a. Lng tnh song - hat cua anh sang
Trc y, ngi ta coi nng lng co tnh cht lin tuc,
qua trnh phat va hp thu nng lng co tnh cht lin tuc.
Nm 1900, giai thch cac qui lut v hp thu va phat xa
cua cac vt en tuyt i nha vt ly hoc c M.Planck a
phat biu gia thuyt: Nng lng bc xa c giai phong
hoc hp thu di dang nhng lng gian oan goi la
cac lng t nng lng. Vi tia n sc co tn s va
bc song th lng t nng lng co tr s bng:

c
h h
(h la hng s Planck co gia tr bng
6,6256.10
-34
J.s ) (2-2)
Ngay nay khai nim lng t nng lng la mt trong
nhng khai nim c ban quan trong nht cua khoa hoc t
nhin.
Cac bng chng thc nghim chng to anh sang co
lng tnh song - hat.
Ban cht song cua anh sang th hin trong cac hin
tng nhiu xa va giao thoa, trong o anh sang th hin
tnh cht nh nhng song truyn i trong khng gian vi vn
tc c va bc song , tn s xac nh. = h = hc/
Ban cht hat cua anh sang th hin : hiu
ng quang in; hiu ng Compton. Trong cac hiu ng nay,
anh sang th hin tnh cht nh cac dong hat co khi
lng va xung lng xac nh vi ng nng tnh bng cng
thc: = mc
2
(m la khi lng hat anh sang; c la vn tc
truyn anh sang). S
thng nht tnh cht hat va song cua anh sang dn n
4
h thc Einstein biu din mi quan h gia khi lng
(m) vi tn s (): = h =hc/= mc
2
, do o co: =
mc
h
b.
Tnh cht song cua cac hat vi m
Nm 1924 nha vt ly hoc Phap Louis de Broglie m rng
quan nim v lng tnh song - hat bng gia thuyt: moi
hat vt cht (chng han e) chuyn ng u co th coi
nh qua trnh song c trng bng bc song c tnh
theo h thc De Broglie: =
mv
h
; trong o: m la khi lng
hat; v la vn tc chuyn ng cua hat.
(2-8)
Nguyn ly bt nh. T tnh cht song cua cac hat vi
m, nm 1927 nha vt ly c W.Heisenberg chng minh c
nguyn ly bt nh: v nguyn tc khng th xac nh ng
thi chnh xac ca toa va vn tc cua hat, do o khng
th ve hoan toan chnh xac quy ao chuyn ng cua hat.
T o co th chng minh ra h thc bt nh:
m
h
v . x
x

(2-9)
trong o: x la sai s cua phep o toa theo phng x
v
x
la sai s cua phep o thanh phn vn tc
cua hat theo phng x
m la khi lng cua hat; h la hng s Planck.
c. Khai nim v c hoc lng t
Ham song: Do cac hat vi m co tnh cht song nn
trang thai chuyn ng cua hat vi m c m ta bng
mt ham s phu thuc toa va thi gian - goi la ham
song - k hiu (x, y, z, t) hay (q, t).
Ham song co th la ham thc hay ham phc, co y ngha
vt ly nh sau: (q, t)
2
dxdydz cho bit xac sut tm thy
hat tai thi im t, trong nguyn t th tch d= dxdydz co
tm la M(x,y,z). Trong c hoc lng t khng con khai nim
quy ao nn ngi ta tm cach xac nh xac sut tm thy
hat cac im khac nhau trong khng gian. V xac sut tm
thy hat trong toan b khng gian la bng 1 nn:
1 d
2

.
iu kin nay c goi la iu kin chun hoa cua ham
song
Nu trang thai cua hat khng phu thuc thi gian (c
goi la trang thai dng) th ham song khng phu thuc thi
gian t. Khi o (q)
2
biu th mt xac sut tm thy hat
tai im co toa q, ch phu thuc vao toa (q la k
hiu tng quat ch toa ).
B y u cac ai lng vt ly. Trang thai xac
nh cua hat c m ta bng ham song (q). Khi o mt
s ai lng vt l c trng cho trang thai cua hat cung
co gia tr xac nh. S ai lng vt l c lp vi nhau
5
(tc la khng phai la ham cua nhau) lp thanh b y u
cac ai lng vt l c trng cho trang thai cua hat.
Phng trnh Schrodinger. tm c ham song
ngi ta giai phng trnh song, con goi la phng trnh
Schrodinger. Phng trnh nay c xem nh nguyn ly c ban
cua c hoc lng t , do Schrodinger thit lp ln u tin
vao nm 1926. Trong trng hp tng quat co th vit
phng trnh Schrodinger di dang: E H vi H la toan
t Haminton, E la nng lng.
Phng trnh vi phn cua ham , i vi hat e chuyn
ng trong mt in trng (vi V la th nng va E la nng
lng toan phn cua hat) co dang nh sau

,
_
E V
m 8
h
2
2
; trong o la toan t Laplace :
2
2
x
+
2
2
y
+
2
2
z
.
1.4. NGUYN T CO MT ELECTRON (Nguyn t dang hiro)
1.4.1. Phng trnh Schrodinger
Trong nguyn t, mt cach gn ung, co th coi nh hat
nhn ng yn, trong tm cua h nguyn t trung vi trong
tm cua hat nhn va ly tm hat nhn lam gc toa . Khi
o ta ch xet chuyn ng cua electron trong khng gian, di
tac dung cua in trng gy ra bi in tch cua hat nhn
(trng th co i xng cu). Chuyn ng nay c goi
la chuyn ng Orbital. Khi o phng
trnh Schrodinger c vit nh sau:

,
_
E
r 4
Ze
m 8
h
0
2
2
2
.
Ham la nghim cua cng thc trn
phai thoa man cac iu kin: n tr, lin
tuc, hu han trong toan khng gian.
thun li cho vic giai, do tnh i
xng tm cua trng th, ngi ta s
dung h toa cu (r, , ) thay cho
h toa Descartes (x, y, z). Quan h
gia 2 h toa nh sau (xem hnh
bn).
x = r.sin.sin; y = r.sin.sin; z = r.cos
vi: 0 r , 0 , 0 2
1.4.2. Ham song
Khi giai phng trnh Schrodinger i vi nguyn t 1 electron
dn n vic t: (r, , ) = R(r). Y(, ). Phep giai phng
trnh dn n kt qua:
n.l.m
(r, , ) = R
n.l
(r). Y
l.m
(, ).
6
x
y
z
0
M
r
M
Phn xuyn tm R(r) cua ham song phu thuc vao cac tham
s n va l ; n c goi la s lng t chnh, l c goi la
s lng t th 2 (con goi la s lng t phu hay s
lng t momen ng lng orbital). l = 0, 1, 2 ... (n - 1).
Phn goc cua ham song: Y (, ) phu thuc vao tham s m
vi m = 0, t1, t2, ..., t l. m c goi la s lng t t hay
s lng t hnh chiu momen orbital.
Cac ham ring tc la nghim cua phng trnh H = E
c goi la cac orbital nguyn t (Ky hiu la A.O. vit tt
cua Atomic Orbital).
1.4.3. Cac ai lng vt ly c trng cho trang thai
cua e trong nguyn t
Trang thai chuyn ng trong khng gian (chuyn ng
orbital) cua electron c c trng bi nng lng E, momen
ng lng orbital
M
va hnh chiu cua momen ng
lng orbital ln truc z: M
Z
. Vic tm nhng nghim thoa
man cac iu kin n tr, gii ni va lin tuc cua ham song
lam xut hin nhng tham s nguyn, goi la cac s lng
t.
a. Nng lng cua electron trong nguyn t c xac
nh bi biu thc:
2
n
n
1
E
.
2 2
0
4 2
h 8
e mZ
, trong o n = 1, 2, 3, ... va c goi la

s lng t chnh.
V n la nhng s nguyn dng nn nng lng cua e trong
nguyn t ch co th nhn nhng gia tr gian oan, o la
s lng t hoa nng lng. ng vi mi gia tr n ta co
mt lp e (ng vi mt mc nng lng nht nh) va
c k hiu nh sau:
n : 1 2 3 4 5 6
7 ...
Mc E
n
: K L M N O P
Q ...
khi n cang ln tr s E
n
cang cao (cang gn 0) va hiu gia 2
mc lin tip cang nho. Khi electron chuyn t mc n v
mc n, se phat ra mt bc xa co lng t nng lng
bng h = E = E
n
- E
n
. i vi nguyn t hiro Z = 1 nn ta co:
2
n
n
1
E
.

2 2
0
4
h 8
me

2
n
6 , 13
(eV).
b. ln cua momen ng lng orbital c xac nh
bi biu thc:

M
=
) 1 l ( l +
.
2
h
; trong o: l = 0,1, 2, 3, ... , (n -1) va
c goi la s lng t phu.
V l ch co th nhn nhng gia tr nguyn nn
M
ch co
th nhn nhng gia tr gian oan, o la s lng t hoa
momen ng lng. Nhng electron ng vi cung mt mc
7
nng lng E
n
co th co n gia tr khac nhau cua
M
. Tai lp
th n, ta co n phn vi cac tr s khac nhau cua l va c k
hiu tng ng nh sau:
Gia tr cua l : 0 1 2 3 4 5 6 7
8
Trang thai (phn lp) : s p d f g h I
k l
c. Hnh chiu cua momen ng lng orbital ln truc z
(M
Z
) c tnh bng cng thc:
2
h
m M
Z
trong o: m = 0, t1, t2, ...., tl va c goi la
s lng t t. (2-17) .
M
z
ch co th nhn nhng gia tr gian oan ng vi cac
tr s gian oan cua m. Ngha la vect
M
khng th nh
hng mt cach bt ky trong khng gian ma ch co (2l + 1)
cach nh hng cho 1 gia tr cua l. Noi cach khac, tai phn
lp th l co (2l + 1) orbital nguyn t.
d. Spin
Bng ly thuyt va thc nghim ngi ta nhn thy
electron ngoai chuyn ng khng gian quanh ht nhn (c
c trng bng 3 s lng t n, l, m) con co momen ng
lng ring. d hiu, chung ta co th hnh dung electron
co chuyn ng t quay xung quanh 1 truc ring (ging nh
qua t t quay quanh truc), do o sinh ra momen ng
lng spin. Momen ng lng spin co gia tr bng:
) 1 s ( s M
s
+ .
2
h
Trong o h la hng s Planck, s la s lng t spin lun
lun co gia tr bng 1/2.
Nh vy s
M
lun lun co tr s khng i. Vect
s
M ch co
th nh hng theo 2 cach xac nh trong khng gian sao cho
hnh chiu cua no ln truc z co tr s bng:
2
h
m M
S Z , S
s c goi la s lng t t spin co th nhn 1 trong 2
gia tr bng +1/2 va -1/2.
1.4.4. My electron
Ta a bit mt xac sut co mt cua electron tai mt
im co toa q c xac nh bng
2
) q (
. co mt
khai nim trc quan hn ngi ta thng dung khai nim
my electron. My electron c quy c la min khng gian
trong o xac sut co mt cua electron la > 90% va c gii
han bng mt b mt gii han gm cac im co mt
xac sut bng nhau. Hnh dang va kch thc cua my
electron phu thuc vao cac s lng t n, l, m. Trn hnh 1-3
trnh bay hnh dang va s nh hng cac my electron s, p,
d
8
Phn lp s (l = 0) m = 0 (s).
Phn lp p (l = 1) m = +1 (p
X
); m = 0 (p
Z
); m = -1 (p
Y
).
Phn lp d (l = 2) m = +2 (d
x2 - y2
); m = +1 (d
XZ
); m = 0 (d
z2
); m
= -1(d
YZ
); m = -2 (d
XY
);

1.5. NGUYN T NHIU IN T
1.5.1. Phng phap gn ung mt electron
Bai toan v nguyn t co nhiu electron tr nn phc tap
hn nhiu so vi bai toan nguyn t ging hiro. Khi o mi
electron khng nhng chu lc hut cua hat nhn nguyn t
ma con chu lc y cua cac electron khac trong nguyn t.
Hiu ng chn: Cac electron cua lp bn trong co tac
dung chn manh i vi lp bn ngoai. Cac electron co s
lng t l ging nhau th nu n cang tng se co tac dung
chn cang yu nhng b chn cang nhiu. Tac dung chn
cua lp ngoai i vi lp trong khng ang k. Trong cung
mt lp cac electron chn nhau khng manh so vi khi khac
lp. Trong cung mt phn lp cac electron chn nhau cang yu
hn. Theo chiu ns, np, nd, nf tac dung chn yu dn nhng
b chn tng ln. V vy, khi tng in tch hat nhn (Z), th
in tch hat nhn hiu dung tng manh i vi cac
electron p, d, f. Mt phn lp a bao hoa hoan toan electron hay
bao hoa mt na (mi lng t co u mt electron) th
co tac dung chn rt ln i vi cac lp bn ngoai. Hai
electron thuc cung mt lng t chn nhau rt yu
nhng lai y nhau rt manh
Hiu ng xm nhp: theo nguyn l bt nh, electron co
th co mt bt k khu vc nao trong khng gian vi xac
sut ln hay nho, v vy mt electron du thuc lp bn ngoai
vn co mt thi gian nao o tn tai gn khu vc hat
nhn, do o co th noi electron cua lp ngoai a xm nhp
9

z

y

x

z

x

y

z

x

y

z

x

y

x

y

z

y

x

z

z

y

x

y

x

z

x

z

y

Hnh 1-6: Hnh dang va s nh hng
cua my electron.
lam tng bn lin kt gia electron o va hat nhn. o
chnh la hiu ng xm nhp. Hiu ng xm nhp cang ln
khi cac s lng t n va l cua electron cang nho.
V vy, nng lng electron trong trng hp nay khng
nhng phu thuc vao s lng t chnh n ma con phu
thuc vao s lng t phu l. Ngi ta noi co s kh
hin tng suy bin.
i vi nguyn t co N electron, phng trnh Schrodinger
i vi electron i co dang:
) i ( E
r 4
e Z
m 8
h
i i
1 0
2 *
i
1
2
2

,
_
(1-20) vi Z
i
*
= Z -
I
(2-21)
Ham song cua ca nguyn t la: (1,2,..,N) = (1). (2)... (N)
Nng lng cua ca nguyn t: E = E
1
+ E
2
+ ...+ E
N
Hng s chn
I
phu thuc vao ca hnh dang va kch
thc my electron I, (tc la phu thuc vao n, l), nu mt
xac sut co mt cua electron khu vc gn hat nhn
cang ln th
I
cang nho (hiu ng xm nhp), do o nng
lng E
i
khng nhng phu thuc vao s lng t l cua
electron c xet:
2
2 *
2 2
0
4 2 *
2
l , n
n
Z
6 , 13
h 8
e . mZ
.
n
1
E

(2-22)
Ta cung co th s dung cac cach biu din cac AO a
dung i vi cac nguyn t 1 electron. Nng lng cua
electron trong cac AO phu thuc vao hiu ng chn va hiu
ng xm nhp.
1.5.2. Gian nng lng. Quy tc Klechkowsky
Khi nghin cu th t nng lng cua cac AO trong nguyn
t nhiu electron, nha bac hoc Klechkowsky a a ra 2 quy
tc sau:
a. Nng lng E
n,l
tng theo gia tr tng s (n + l).
b. Nu 2 AO co tng (n + l) nh nhau th AO nao co n ln
hn se co nng lng cao hn.
Nng lng cua cac AO: 1s < 2s < 3s < 3p < 4s < 3d < 4p < 5s
< 4d < 5p < 6s < 5f 5d < 6p < 7s < 5f 6d < 7p ....
1.5.3. Khai nim lp, phn lp, lng t
a. Lp electron. Trong mt nguyn t, cac electron co s
lng t chnh (n) ging nhau tao thanh mt lp. Nh vy,
n ch s th t lp electron; cac lp c k hiu nh sau:
S lng t chnh n : 1 2 3 4 5 6 7
K hiu lp : K L M N O P Q
n cang ln th electron co nng lng cang cao va my electron
c phn b cang xa hat nhn.
10
b. Phn lp. Mi lp gm cac phn lp electron co cac s
lng t n, l nh nhau. Cac phn lp c k hiu bng
phn s cua n va phn ch (ch l).
S lng t phu l: 0 1 2 3 4 5 6 7 8
K hiu phn lp: s p d f g h I k l
c. lng t hay orbital nguyn t. Cac electron co 3 s
lng t n, l, m ging nhau ngha la co ham song orbital (q)
ging nhau (trang thai chuyn ng quy ao ging nhau)
th c goi la thuc cung mt lng t.
d. Cach biu din cu tao vo electron cua nguyn t
- Dung cng thc electron. V du: Nit (N): 1s
2
2s
2
2p
3
- Dung k hiu lng t: N: 1s 2s
2p
1.5.4. Cac quy lut phn
b electron trong nguyn t nhiu in t
a. Nguyn l loai tr Pauli
Trong mt nguyn t khng th co hai electron co cung gia
tr 4 s lng t ging nhau. Co ngha la: cac electron trong
mt lng t co 3 s lng t n, l, m ging nhau nn s
lng t t spin (m
s
) phai khac nhau (+1/2 va -1/2). Noi cach
khac, trong mt lng t ch co th co ti a 2 electron
vi spin ngc du.
Trong mt phn lp ng vi s lng t phu l co (2l + 1)
lng t nn co ti a 2(2l + 1) electron. Do vy, s
electron ti a cua cac phn lp nh sau: s
2
, p
6
, d
10
, f
14

Mt lp ng vi s lng t chnh n co n phn lp ng
vi l = 0, 1, 2, ..., (n - 1). Mi phn lp co ti a 2(2l + 1) e nn
s e ti a cua ca lp la:
+
1 n
0 l
2
n 2 ) 1 l 2 ( 2
.
b. Nguyn l vng bn
Trong nguyn t, cac electron phn b vao cac AO co mc
nng lng t thp n cao. Khi o, nguyn t trang thai
bn nht (co mc nng lng thp nht), goi la trang
thai c ban.
Ap dung nguyn l Pauli va nguyn l vng bn co th vit
cng thc electron cho cac nguyn t. V du: Na (Z = 11):
1s
2
2s
2
2p
6
3s
1
Mn (Z = 25): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
2

c. Quy tc Hund
+ Trong mt phn lp cac electron co khuynh hng phn
b u vao cac lng t sao cho s electron c thn la
cc ai (tng spin
co gia tr cc ai).
V du nguyn t oxi:
co Z
O
= 8 nn cu
hnh e la:
11

1s
2

2s
2

2p
4
+ Nu cac phn lp d hay f co cu hnh gn bao hoa hoc
gn na bao hoa th e phn lp sat trn se chuyn v
at cu hnh bao hoa hoc na bao hoa
1.6. NNG LNG ION HOA VA AI LC I VI ELECTRON
1.6.1. Nng lng ion hoa (I)
Nng lng ion hoa la nng lng cn tiu thu tach
mt electron ra khoi nguyn t trang thai c ban va th
kh.
i vi mt nguyn t a cho nng lng ion hoa th
nht la nho nht, sau o n nng lng ion hoa th hai
ri th ba: I
1
< I
2
< I
3
...
1.6.2 Ai lc i vi electron (E)
Ai lc i vi electron la nng lng c giai phong khi
kt hp 1 electron vao mt nguyn t trang thai c ban.
Nguyn t co kha nng thu electron cang manh th ai lc
i vi electron cang ln, v du cua hiro bng 0,75 eV, cua
oxi la 1,47 eV va cua flo la 3,52 eV.
1.7. BIN THIN TUN HOAN TRONG CU TAO CUA CAC
NGUYN T HOA HOC
1.7.1. S tun hoan trong qua tnh xy dng cac lp
electron
Khi sp xp cac nguyn t hoa hoc theo chiu tng dn
cua in tch hat nhn (Z) ngi ta nhn thy s hnh
thanh cac lp electron xay ra mt cach tun hoan nh sau:
c sau mt s nguyn t lai bt u hnh thanh mt lp
electron mi ngha la s hnh thanh cac lp vo electron xay ra
theo tng chu k.
Chu k 1: gm hai nguyn t t Z = 1 n Z = 2.
Z = 1: H: 1s
1
Z = 2: He: 1s
2
Chu k 2: Gm 8 nguyn t t Z = 3 n Z = 10
(Cac electron xy dng thm cac phn lp2, 2p)
Z = 3 Li: 1s
2
2s
1
Z = 4 Be: 1s
2
2s
2
Z = 5 B: 1s
2
2s
2
2p
1
Z = 6 C: 1s
2
2s
2
2p
2
Z = 7 N: 1s
2
2s
2
2p
3
Z = 8 O: 1s
2
2s
2
2p
4
Z = 9 F: 1s
2
2s
2
2p
5
Z = 10 Ne: 1s
2
2s
2
2p
6
Chu k 3: gm 3 nguyn t t Z = 11 n Z = 18
(Cac electron xy dng thm cac phn lp 3s, 3p)
Z = 11 Na: 1s
2
2s
2
2p
6
3s
1

12
.....
Z = 18 Ar: 1s
2
2s
2
2p
6
3s
6

Chu k 4: gm 18 nguyn t t Z= 19 n Z = 36
(Cac electron xy dng thm cac phn lp 4s, 3d va 4p)
Z = 19 K: (Ar) 4s
1
......
Z = 36 Kr: (Ar) 4s
2
3d
10
5p
6
Hay: Kr: (Ar) 3d
10
4s
2
4p
6
(Cac electron xy dng thm cac phn lp 5s, 4d, 5p)
Z = 37 Rb: (Kr) 5s
1
.......
Z = 54 Xe: (Kr) 5s
2
4d
10
5p
6
Hay: (Kr) 4d
10
5s
2
5p
6
(Cac electron xy dng thm cac phn lp 6s, 4f, 5d, 6p)
Z = 55 Cs: (Xe)6s
1
.......
Z = 86 Rn: (Xe)6s
2
4f
14
5d
10
6p
6
Hay: (Kr) 4d
10
4f
14
5s
2
5p
6
5d
10
6s
2
6p
6
Chu k 7: (cha hoan thanh), hin nay ch mi bit 20
nguyn t t Z = 87 n Z = 106.
(Cac electron xy dng thm cac phn lp 7s, 5f, 6d)
Z = 87 Fr: (Rn)7s
1
Z = 88 Ra: (Rn)7s
2
Z = 89 Ac: (Rn)7s
2
6d
1
.......
Z = 106: (Rn)7s
2
5f
14
6d
4
S hnh thanh cac chu k, cac day nguyn t chuyn tip,
cac ho Lantanoit va Actinoit co nguyn nhn quy lut bin
thin nng lng cua cac AO theo in tch hat nhn Z.
1.7.2. Mt s nhn xet
a. Qua trnh hnh thanh vo electron cua cac nguyn t
co tnh cht tun hoan
C sau mt day nguyn t lai bt u xy dng mt
lp electron mi. Day nguyn t trong o ang hnh thanh mt
lp electron mi c goi la mt chu k. Bt u chu k n la
nguyn t tai o bt u xy dng phn lp ns. Kt thuc chu
k la nguyn t tai o electron bao hoa phn lp np. Tuy nhin
tnh tun hoan trong cu tao nguyn t khng th hin
mt cach n gian ma co s phat trin. Chu k u ch co
hai nguyn t (xy dng phn lp 1s), cac chu k 2 va 3 mi
chu k co 8 nguyn t (xy dng phn lp 2s, 2p va 3s, 3p) cac
chu k 4 va 5 mi chu k co 18 nguyn t, chu k 6 co 32
nguyn t...Nguyn nhn cua s phat trin xoay trn c nay
bt ngun t quy lut phn b electron trong nguyn t.
13
b. S sp xp electron vao cac phn lp noi chung
phu hp vi quy tc Klechkowsky nhng co mt s
ngoai l.
Sau V (Z = 23) vi cac phn lp ngoai la 3d
3
4s
2
ang le co Cr
(Z = 24) 3d
4
4s
2
nhng lai co 3d
5
4s
1
v cu truc in 1/2
lng t co tnh bn cao hn. Trng hp tng t xay ra
vi Mo (Z = 42)
Sau Ni (Z = 28) vi cac phn lp ngoai la 3d
8
4s
2
ang le co
Cu (Z = 29) 3d
9
4s
2
nhng lai co 3d
10
4s
1
v cu truc sau bn
hn. Cac trng hp tng t xay ra vi Ag (Z = 47), Au (Z =
79). Hin tng nay thng c goi la s vi bao hoa
phn lp d.
Ho Lantanoit bt u bng La (Z = 57) co cac phn lp
ngoai: 5s
2
5p
6
5d
1
6s
2
. Sau o n Ce (Z = 58) electron khng
xp vao 5d ma xy dng 4f. 5s
2
5p
6
6s
2
4f
2
. cac nguyn t
tip theo (t Pr: Z = 59 n Lu: Z = 71) cac electron tip tuc
xy dng phn lp 4f cho n bao hoa ma khng xp vao 5d
(tr Gd: Z = 64). Ch tr Hf (Z = 72) electron mi lai tip tuc
xy dng 5d.
S xy dng vo electron cua cac nguyn t trong ho
Actinoit xay ra cung khng tun theo quy tc Klechkowsky. Cac
trng hp bt thng cung xay ra vi cac nguyn t Ru (Z
= 44), Rh (Z = 45), Pd(Z = 46).
1.7.3. Bang h thng tun hoan cac nguyn t hoa
hoc
Vao gia the k 19, khi nghin cu s bin thin tnh cht
cua nguyn t va hp cht cua chung theo chiu tng cua
khi lng nguyn t va tm cach phn loai cac nguyn t,
nha bac hoc Nga .I Meneleev a kham pha ra nh lut
tun hoan (nm 1869) va trn c s o Meneleep a xp 63
nguyn t a bit luc o thanh h thng tun hoan la h
thng tun hoan. Ngay nay, di anh sang cua l thuyt
cu tao nguyn t, nh lut tun hoan c phat biu
nh sau: tnh cht cua cac nguyn t va tnh cht cua cac
n cht, hp cht cua cac nguyn t phu thuc tun
hoan vao in tch hat nhn.
a. Nguyn tc xy dng bang h thng tun hoan
Cac nguyn t c xp theo chiu tng dn cua in tch
hat nhn (Z). Cac nguyn t trong chu k c xp thanh 1
hay nhiu hang ngang.
Cac nguyn t thuc nhng chu k khac nhau nhng co tnh
cht ging nhau c xp thanh mt ct trong bang. S
ch nhom bng mc oxi hoa (hay s oxy hoa) cao nht cua
cac nguyn t trong bang (tr mt s ngoai l).
b. Mt s dang bang h thng tun hoan
Dang bang dai: Cac nguyn t trong mi chu k c xp
thanh mt hang.
14
Toan bang co 16 nhom anh s t IA, IIA, ..., VIIIA va IB,
IIB, .., VIIIB. Hai ho Lantanit va Actinit gm cac nguyn t f
c xp vao nhom IIIB. Nhom A gm cac nguyn t s, p;
Nhom B gm cac nguyn t d, f.
Dang bang ngn: Chu k nho co 1 hang, chu k ln co hai
hang.
Toan bang co 8 nhom, mi nhom chia thanh 2 phn nhom.
Phn nhom chnh gm cac nguyn t s, p. Phn nhom phu
gm cac nguyn t d,f.
S phat trin cua khoa hoc hin ai cho phep tm ra
nhiu nguyn t mi va hiu su sc, chnh xac va y u
hn tnh cht va cac hp cht cua chung. nh lut tun
hoan va cac ng dung cua no co vai tro quan trong trong
nhiu lnh vc khoa hoc va c nhiu nha khoa hoc
cac chuyn nganh khac quan tm n. V vy, hin nay co
nhiu cach biu din h thng tun hoan. a co ti gn
100 dang bang, th hoc m hnh biu din nh lut
tun hoan nhng chung ta ch xet hai dang bang c ph
bin rng rai nht.
c. S bin thin tun hoan tnh cht cua cac nguyn
t hoa hoc
Phn ln tnh cht cua cac cht mc nhiu hay t
u phu thuc vao cu tao v electron cua nguyn t nn
phu thuc tun hoan vao in tch hat nhn.
Nng lng ion hoa. Trong mi chu k, nguyn t u chu
k (kimloai kim) co nng lng ion hoa thp nht, nguyn
t kh tr kt thuc chu k co nng lng ion hoa cao nht.
Ai lc vi electron. Noi chung, trong mt chu k, ai lc vi
electron tng ln khi tin dn n nhom VIIA. Cac nguyn t
halogen co ai lc vi electron cao nht.
Ban knh nguyn t. Cung bin thin tun hoan theo chiu
tng cua Z. Cac kim loai kim co ban knh nguyn t ln
nht, cac kh tr co ban knh nguyn t nho nht.
Mc oxy hoa (hay s oxy hoa). Mc oxy hoa dng c
tnh bng s electron tach ra khoi nguyn t khi hnh thanh
lin kt ion hay lin kt cng hoa tr co cc. Mc oxy hoa
m c tnh bng s electron ma nguyn t nhn vao.
Mc oxy hoa cao nht cua nguyn t noi chung phu hp vi
s ch nhom nguyn t.
========================
15
CHNG 2
LIN KT HOA HOC VA
CU TAO PHN T
2.1. CAC C TRNG C BAN CUA LIN KT HOA HOC
2.1.1. Nng lng lin kt: La nng lng c giai
phong khi hnh thanh mi lin kt hoa hoc gia cac nguyn
t c lp. Nng lng lin kt co th co th tnh ra eV/phn
t hay kJ.mol
-1
hay kCal.mol
-1
. (1 eV = 4,3360.10
-8
kcal; 1 kcal =
4,1840 kJ). V du: lin kt H H co nng lng bng -414,4
kJ/mol
2.1.2. dai lin kt: La khoang cach gia tm cua hai
nguyn t tham gia lin kt. (Tnh ra anstron (A
0
), 1A
0
= 10
-8
cm;
V du: dai lin kt H - H la 0,74 A
0
).
2.1.3. Goc hoa tr: La goc tao bi hai mi lin kt cung
mt nguyn t vi hai nguyn t khac. V du trong phn t
nc goc hoa tr HOH la 104,5
0
.
2.1.4. bi lin kt: La s mi lin kt c hnh
thanh gia hai nguyn t cho trc. V du trong phn t Nit
bi cua lin kt bng 3: NN
2.2. M IN CUA NGUYN T
Khi hnh thanh lin kt hoa hoc cua cac nguyn t tham gia
lin kt trao i electron hoa tr vi nhau (nhng electron cho
nhau hay gop chung electron). Khi o chiu di chuyn cua
electron hoa tr c xac nh so sanh m in cua hai
nguyn t.
ai lng:
2
I E +

c goi la m in cua
nguyn t. Trong o: E la ai lc vi electron, I la nng lng
ion hoa cua nguyn t o.
Nh vy: khi hnh thanh mi lin kt hoa hoc gia hai
nguyn t, electron hoa tr chuyn t nguyn t co m
in nho sang nguyn t co m in ln. Ngi ta
thng tnh m in ra n v qui c, khi o chp nhn
m in cua flo bng 4 n v.
Bang 2.1: m in cua mt s nguyn t
H (2,1)
Li (0,98) Be (1,5) B (2,0) C (2,5) N (3,07) O (3,5) F (4,0)
Na
(0,93)
Mg (1,2) Al (1,6) Si (1,8) P (2,2) S (2,6) Cl (3,0)
K (0,91) Ca
(1,04)
Ga
(1,8)
Ge
(1,8)
As (2,1) Se (2,5) Br (2,8)
Rb (0,89 Sr (1,0) In (1,5) Sn Sb (1,8) Te (2,1) I (2,6)
16
(1,8)
Cs ( ) Ba
(0,99)
Tl ( ) Pb ( ) Bi ( ) Po ( )
Da vao m in ngi ta phn bit cac dang lin kt
c ban:
+ Nu hai nguyn t tham gia lin kt co m in khac
xa nhau ( 2) th my electron lin kt gn nh b di chuyn
hoan toan v pha nguyn t co m in ln. Khi o hnh
thanh lin kt ion.
+ Nu hai nguyn t tham gia lin kt co m in bng
nhau th my electron lin kt c phn b u gia hai
nguyn t va hnh thanh lin kt cng hoa tr khng phn
cc.
+ Nu hai nguyn t tham gia lin kt co m in khac
nhau khng nhiu ( < 2) th hnh thanh lin kt cng hoa tr
phn cc.
2.3. LIN KT ION
iu kin tao thanh lin kt ion la hai nguyn t tham gia
lin kt co m in khac nhau nhiu: 2. Khi o my
electron lin kt se chuyn hoan toan v pha nguyn t co
m in ln va lam cho nguyn t nay tr thanh ion m,
nguyn t kia tr thanh ion dng. Hai nguyn t lin kt vi
nhau bng lc hut tnh in.
Hoa tr cua nguyn t trong lin kt ion dung dch tnh bng
s electron hoa tr ma nguyn t nhng ra hay thu vao. Khi
nguyn t nhng electron bin thanh ion dng th no co
hoa tr dng. Khi nguyn t thu electron bin thanh ion m
th co hoa tr m.
V du: Khi hnh thanh lin kt Na
+
Cl
-
th Natri co hoa tr +1,
clo co hoa 1-.
Nng lng cua lin kt ion la nng lng tng tac tnh
in gi hai ion gm co:
+ Nng lng hut cua 2 in tch ngc du cua hai ion
c tnh bng cng thc Culong:
r
e Z Z
k U
2
2 1
hut
k la
h s t l phu thuc vao cach chon n v. (3-2)
+ Nng lng y gia hai vo e cua hai ion, tng tac y
ch ang k khi hai ion tin sat gn nhau, my electron cua hai
ion bt u tip xuc nhau.
n
2
y
r
e . B
U (3-3)
B la hng s, n la h s Born co gia tr phu thuc vao
dang cu truc vo e cua ion.
Tng nng lng tng tac gia hai ion: U = U
hut
+U
y
.
Lin kt ng vi gia tr m nht cua U khi khoang cach gia
hai tm cua hai ion bng r
0
17
Lin kt ion co c im khng bao hoa, va khng co tnh
nh hng. V vy, cac hp cht ion thng tao thanh cac
tinh th ion, v du mui, oxit kim loai, hiroxit kim loai.
2.4. LIN KT CNG HOA TR
2.4.1. PHNG PHAP CNG HOA TR (PHNG PHAP VB)
a. Bai toan phn t hiro
Khi ap dung c hoc lng t giai quyt vn ban
cht lin kt hoa hoc, nm 1927 hai nha bac hoc W.Heiter va
F.London a giai bai toan tnh nng lng lin kt trong phn
t hiro (H
2
). Kt qua bai toan cho thy lin kt gia 2
nguyn t hiro c hnh thanh khi hai electron cua 2 nguyn
t hiro co spin ngc chiu nhau, tc la m
s
= +1/2 va m
s
=
-1/2.
Khi hnh thanh lin kt, mt my electron khu vc
khng gian gia hai hat nhn tng ln ging nh hai am my
xen phu ln nhau. Do o mt in tch m khu vc o
tng ln, iu nay co tac dung hut hai hat nhn lai va lin
kt chung lai vi nhau.
Khai quat hoa cac kt qua trn chung ta i n nhng tin
c ban cua phng phap cp electron lin kt.
b. Nhng lun im c ban cua phng phap cp
electron lin kt
a. Lin kt cng hoa tr c hnh thanh do s ghep i
hai electron c thn co s lng t m
s
ngc du nhau
cua hai nguyn t tham gia lin kt vao mt lng t cua
phn t (mt orbital phn t). Khi o xay ra s xen phu gia
hai my electron lin kt.
b. Mc xen phu gia hai my electron cang manh th lin
kt cang bn.
c. Lin kt c phn b theo phng tai o xen phu ln
nhau gia cac my electron lin kt la ln nht.
c. Hoa tr cua nguyn t trong lin kt cng hoa tr
V lin kt cng hoa tr c hnh thanh do s ghep i hai
electron c thn cng hoa tr cua mt nguyn t c tnh
bng s electron c thn cua nguyn t khi trang thai t
do (trang thai c ban hay kch thch).

V du: 1s
nguyn t hiro co hoa tr
bng 1:
Nguyn t He co hoa tr
bng 0
Li co hoa tr bng 1:
18

2
s

Be trang thai c ban: hoa tr la 0:
Trang thai kch thch: 1s
2
2s
1
2p
1
:
d. Lin kt cho nhn
Xet s hnh thanh ion NH
4
+
t phn t NH
3
va ion H
+
: NH
3
+
H
+
NH
4
+
Nguyn t N trong phn t NH
3
a tao thanh 3 mi lin kt
cng hoa tr vi 3 nguyn t hiro, con co mt cp electron
cha dung n goi la cp electron khng phn chia.
Ion H
+
co lng t trng 1s. Khi ion H
+
tin n gn
phn t NH
3
, cp electron khng phn chia cua nguyn t N b
ion H
+
va tr thanh cp electron chung cho ca hai nguyn t:
Mi lin kt c hnh thanh nh cp electron khng phn
chia cua 1 nguyn t va lng t trng cua nguyn t kia
c goi la lin kt cho nhn hay con goi la lin kt phi
tr hoc lin kt ban cc. Nguyn t co cp electron khng
phn chia c goi la nguyn t cho, nguyn t co lng
t trng goi la nguyn t nhn.
Co th biu din mi lin kt cho - nhn bng mui tn:
Mt s v du khac:
e. Cng hoa tr cc ai cua nguyn t
V lin kt cng hoa tr khng ch c
hnh thanh nh ghep i cac electron c thn ma con nh cac
cp electron khng phn chia va nh cac lng t trng.
T o, co th rut ra kt lun: s lin kt cng hoa tr ma
nguyn t co kha nng tao thanh bng s lng t
(orbital) cua nguyn t co kha nng tham gia tao lin kt.
i vi cac nguyn t thuc chu k tip theo ngoai cac
lng t ns va np con co mt s lng t (n - 1)d tham
gia tao lin kt, do o cng hoa tr cc ai cua cac nguyn
t nay ln hn 4.
f. Tnh nh hng cua lin kt cng hoa tr va cu
hnh hnh hoc cua phn t
Cac mi lin kt cng hoa tr trong phn t c phn b
theo nhng phng sao cho s xen phu ln nhau cua cac my
electron lin kt la cc ai, v vy hnh dang cac my
19
: N
..
..

H
H
H
+ H
+
H
H
H

..
..
: N H :
+

N
H
H
H
H
+

B
H
H
H
H
+
O N N C
O
electron tham gia lin kt co anh hng quyt nh n cu
truc hnh hoc cua phn t.
Phn t hai nguyn t
Trng hp lin kt s-s: cac my electron s co dang i
xng cu nn mc xen phu gia hai my ch phu thuc
vao khoang cach gia cac hat nhn cua 2 nguyn t va khng
phu thuc vao cach nh hng gia cac nguyn t o.
Trng hp lin kt s-p: v my electron p co hnh dang
qua ta nh hng theo mt phng xac nh (truc x hoc
truc y hoc truc amnic) nn mun co s xen phu cc
ai vi my electron s cua nguyn t th hai th nguyn t
th hai nay phai nm v tr trn truc i xng cua my
electron p cua nguyn t th nht. Hnh 6.
Trng hp lin kt p-p: mun co xen phu cc ai th
hai nguyn t tham gia lin kt phai nh hng sao cho truc
i xng cua hai my electron lin kt p o trung ln nhau.
V mc xen phu: nu quy c ln xen phu s-s
bng 1 th ln xen phu cua lin kt s-p va 3 va cua lin
kt p-p la 3. bn cua lin kt ty l vi mc xen phu.
Trng hp phn t 3 nguyn t
V du xet phn t H
2
S. Hai mi lin kt S-H c thc
hin nh 2 my electron 3p cua nguyn t S vi hai my
electron 1s cua hai nguyn t H. V hai my 3p cua nguyn t S
nh hng vung goc vi nhau nn goc gia hai mi lin kt
S-H la 90
0
(hnh 8). Thc nghim cho bit goc nay bng 92
0
hi ln hn 90
0
. iu nay c giai thch do tnh phn cc
cua lin kt S-H la cho hai nguyn t H tch in dng va
y ln nhau.
Mt cach tng t co th giai thch cu tao hnh hoc
cua phn t H
2
O vi goc gia hai lin kt O-H bng 104,5
0
.
Phn t 4 nguyn t
V du, phn t NH
3
co 3 mi lin kt N-H c thc hin
bi 3 my electron p cua nguyn t N va 3 my electron s cua
nguyn t H, v vy phn t NH
3
cu tao thap tam giac,
nguyn t N nh thap, goc gia hai lin kt bng 107,3
0
.
g.
Thuyt lai hoa
S lai hoa cac my electron
20
H
H
Hnh 2.1. Cu tao
cua phn t H
2
S
S
H
H
H
H
H
Hnh 2.2. Cac mi lin kt
C-H trong phn t CH
4
H
S
C
Xet phn t CH
4
. Trong phn t nay co 4 mi lin kt C-H
c tao thanh bi 4 my electron hoa tr cua nguyn t C la
2s
1
, 2p
3
va 4 my electron cua nguyn t H. Nh vy, ang le
trong phn t CH
4
phai co hai loai lin kt khac nhau: 1 lin
kt s-s va 3 lin kt s-p. Tuy nhin, thc nghim cho bit 4
mi lin kt C-H trong phn t CH
4
u ging ht nhau va
c nh hng i mt vi nhau nhng goc bng 109
0
28
theo cac phng t tm n 4 nh cua hnh t din u.
(hnh 3.2.).
Cac kiu lai hoa
+ Lai hoa sp: mt my s trn ln vi mt my p tao thanh
2 my q nm thng hang vi nhau nhng hng v hai pha
i nhau. V du nguyn t Be trong phn t BeCl
2
.
+ Lai hoa sp
2
: mt my s trn ln vi 2 my p tao thanh 3
my q nm trong mt mt phng tao
vi nhau nhng goc bng 120
0
. V du B trong phn t BCl
3
.

Hnh 2.4. Lai hoa sp
2
+ Lai hoa sp
3
: mt my s trn ln vi 3 my p tao thanh 4
my q nh hng theo phng t tm n 4 nh cua hnh
t din u. V du nguyn t O trong phn t H
2
O, nguyn
t N trong phn t NH
3
, NH
4
+
, nguyn t C trong phn t CH
4
.
1
0
9

2
8
o
'
iu kin lai
hoa cua nguyn t bn la:
- Nng lng cua cac orbital tham gia lai hoa phai xp x
nhau.
- Mt electron cua AO tham gia lai hoa phai u ln.
- xen phu cua cac AO lai hoa vi cac AO cua cac nguyn
t khac tham gia lin kt phai u ln tao thanh lin kt
bn.
21
Hnh 2.5. Lai hoa sp
3
trong phn
t CH
4
1
2
0
0
180
0
Hnh 2.3. Lai
hoa sp
T cac iu kin trn ta co th thy: trong mt chu k
hiu nng lng cua AO - s vi AO - p tng ln khi i t u
n cui chu k nn kha nng tham gia lai hoa giam xung. Khi
tng kch thc nguyn t, kha nng lai hoa cua cac AO hoa
tr giam xung.
h. Lin kt bi - Cac dang lin kt ,
Lin kt c tao thanh khi cac my electron lin kt xen
phu nhau. Nu xen phu cc ai nm trn truc ni hai hat
nhn va nhn truc ni hai hat nhn nguyn t lam truc i
xng th lin kt nay c goi la lin kt .
Nu gia hai nguyn t xut hin lin kt i hoc lin
kt ba th mi lin kt th hai, th ba do cac my electron p
con lai nh hng theo phng vung goc vi truc ni gia
hai hat nhn nguyn t cac my electron p nay xen phu vi
nhau hai bn truc lin kt. Nhng mi lin kt nay c
goi la lin kt .
Lin kt tao thanh trong nhng phn t co lin kt bi.
V du: trong phn t N
2
co 1 mi lin kt va 2 mi lin kt
. Gia hai nguyn t C trong phn t C
2
H
4
co mt mi lin
kt va mt mi lin kt , con trong phn t C
2
H
2
co mt
mi lin kt va hai mi lin kt .
2.4.2. PHNG PHAP ORBITAL PHN T (PHNG PHAP MO)
Phng phap cp electron lin kt tuy ap dung co kt qua
cho nhiu phn t nhng con nhiu trng hp khng th
giai thch c bng phng phap nay. V du s tao
thanh phn thanh phn t ion H
2
+
hoc tnh thun t cua kh
oxi... V vy, hin nay mt phng phap khac c s
dung rng rai hn o la phng phap MO (molecular orbital).
a. T tng c ban cua phng phap MO
Mi electron trong phn t c coi nh chuyn ng trong
mt in trng do cac hat nhn nguyn t va cac electron
con lai gy ra. Trang thai mi electron c m ta bng
mt ham song goi la orbital phn t (MO). Trang thai cua
toan b phn t c xac nh bi ham song toan phn
cua phn t. Bai toan phn t quy v vic xac nh cac MO
va cac mc nng lng tng ng cua chung. Sau o sp
xp electron vao cac MO theo nhng quy tc thch hp
thu c cu hnh electron cua phn t.
Trong phep gn ung th nht (gn ung Born - Oppen -
Heimer) ngi ta coi cac hat nhn la ng yn va giai phng
trnh Schrodinger: H = E trong o H la toan t Hamilton, E la
tr ring cua nng lng, la ham s ring m ta trang thai 1
electron.
Ta se ln lt khao sat cac phn t t n gian n
phc tap.
22
b. Phn t 2 nguyn t co hat nhn ging nhau (phn
t ng hach)
Phn t H
2
+
. Ta co th giai thch chnh xac bai toan c
hoc lng t cho phn t nay. T hnh 2.6. ta vit
c biu thc toan t Hamilton:
Phng trnh
Schrodinger:
H = E vi
,
_
+
r
1
r
1
r
1
4
e
m 2
h
H
2 1 0
2 2
(3-5)
lp MO ngi ta dung phng phap t hp tuyn tnh
cac orbital nguyn t (AO) da trn quan nim sau: trong phn
t hai hat nhn 1, 2 nm cach nhau mt khoang cach r xac
nh. Khi electron chuyn ng gn hat nhn 1, no chu tac
dung chu yu cua hat nhn 1 va trang thai electron c
m ta bi ham song
1
cua nguyn t th 1 (
1
la ham song 1s
cua nguyn t 1) nhng chu mtt nhiu loan nao o gy ra
bi hat nhn t hai nn phai co mt s hang b sung vao
biu thc cua MO. Tng t nh vy, khi electron chuyn
ng gn hat nhn th 2 (la ham 1s cua nguyn t th 2)
co b sung mt s hang biu th s nhiu loan gy ra bi
hat nhn th 1. T o ta co th xem MO nh t hp
tuyn tnh cua cac AO
1
va
2
. Ta co: = a
1
1
+ a
2
2
. Cac h
s a
1
va a
2
la trong lng thng k cua
1
va
2
. a
1
2
va a
2
2
la
xac sut electron trong phn t c m ta bi
1
hay
2
.
Do iu kin chun hoa:
+ + 1 S a a 2 a a d
2 1
2
2
2
1
2
Cui cung ta tm c biu thc cua 2 ham song MO:
S
E voi ung
S +
+
+
+

+ +
1
.... .. )..... (
) 1 ( 2
1
2 1

S
E voi ung
S +

+
1
.... . )... (
) 1 ( 2
1
2 1

Nu bo qua tch phn phu S, ta c biu thc:
) (
2
1
) (
2
1
2 1
2 1

+
+
+

+
+
E
E
Vic nghin cu l thuyt cho thy = 2S, S dng, , m.
MO lin kt va MO phan lin kt
23

-e
r + e + e
1
r
1
r
2
Hnh 2.6. phn t H
2
+
Ngi ta goi ham song MO
+
(tng ng vi nng lng
E
+
) la orbital phn t lin kt. Ham
-
(tng ng E
-
) la MO
phan lin kt.
Ca hai ham MO i xng vi hai truc ni 2 hat nhn va
c coi la thuc dang . Cac MO c xy dng t cac
AO s, c k hiu la
s
i vi MO lin kt va
s
*
i vi MO
phan lin kt. Nh vy, khi t hp 2AO s co cung nng
lng cua hai nguyn t se cho 2 MO: mt MO lin kt
s
co
nng lng thp hn va mt MO phan lin kt co
2
*
co nng
lng cao hn.
Gian cac MO
Hnh 15: biu din s t hp 2 AO 1s thanh 2 MO
s
*
va
s
vi cac mc nng lng cua 2 MO la mc - va mc + .
S phn b electron vao cac MO: cung tun theo nhng quy
tc nh trong nguyn t.
+ Nguyn l vng bn: cac electron ln lt xp vao
cac MO co mc nng lng t thp n cao.
+ Nguyn l Pauli: trong mt MO ch co th co ti a 2
electron co spin i song vi nhau. (m
s
= + 1/2 va m
s
= -1/2)
+ Quy tc Hund: khi electron xp vao cac MO co cung mc
nng lng th khuynh hng chim mt s ln MO sao cho
s electron c thn cc ai.
Cac c trng cua lin kt cng hoa tr trong
phng phap MO
S lin kt ( bi cua lin kt)
) n n (
2
1
N
*

(3.6)
Trong o: n va la s electron nm MO lin kt va MO
phan lin kt.
Nng lng lin k t cang ln (lin kt cang bn) va
dai lin kt cang nho khi ch s lin kt cang ln.
Tng quat v cac phn t co hai hat nhn ging
nhau
24
E
1
s
1
s
s
*
s
-
-
-
-
E
0
r
0
E
-
E
+
r
Hnh 2.7. th E
+

va E
-
theo r
Hnh 2.8. Gian
cac MO
Trong trng hp tng quat, cac AO hoa tr co th la s, p (va
ca d,f). i vi cac nguyn t thuc chu k 2, ch phai xet cac
AO hoa tr 2s, 2p. Gian cac MO. T 8 AO (2s, 2p
x
, 2p
y
, 2p
z
cua 2 nguyn t) ta xy dng c 8 MO trong o 4 MO lin
kt va 4 MO phan lin kt.
Cac th t nng lng cua cac MO c biu din
trn hnh ve sau.
i vi 5 nguyn t u chu k 2 (t Li, Be, B, C, N), do mc
nng lng cua cac AO 2s va 2p tng i gn nhau nn cac
AO 2s va 2p
z
co th cung tham gia t hp tao thanh MO,
iu o co th coi nh s y ln nhau gia hai mc nng
lng:
2s
*
va
2pz
dn n th t nng lng cua cac MO
nh sau:
2s
<
2s
*
<
2px
=
2py
<
2pz
<
2px
*
=
2py
*
<
2pz
*
.
i vi 2 nguyn t cui chu k 2 (O
2
, F
2
), do mc nng
lng cua cac AO 2s va 2p cach xa nhau nn nng lng cua
cac MO nh sau:
2s
<
2s
*
<
2pz
<
2px
=
2py
<
2px
*
=
2py
*
<
2pz
*
.
c. Phn t hai nguyn t co hat nhn khac nhau
xy dng cac MO cho cac phn t AB ta cung t hp
tuyn tnh cac AO hoa tr 2 cua nguyn t A va B phu hp
vi quy tc i xng va lp c gian cac MO ri sp
xp electron vao cac MO o co c cu truc electron
cua phn t va tnh c bc lin kt N.
Gian MO cua phn t CO
25
2p 2p
p
*
x
*

y
*
x

y
2s 2s
s
*
s
2s
2p 2p
p
*
x
*

y
*
x

y
2s
s
*
s
Hnh 2.9. Th t cac MO trong phn t hai
nguyn t A
2
Phn t CO co cu truc electron:
s
2
s
*2
p
2
x
2
=
y
2
(ging
phn t N
2
)
bi N = 3, = 1,13 A
0
, Nng lng lin kt E = -1072
kJ/mol va = 0,12D
(Gian MO cua ion CN
-
cung co cu truc electron tng
t phn t CO).
Gian MO cua phn t NO. Cu truc electron:
s
2
s
*2
p
2
x
2
=
y
2

*1
bi N = 2,5; l = 1,15; Nng lng lin kt E = - 678
kJ/mol, = 0,15D.
Gian MO cua phn t H - F: m in
f
= 4 >
H
= 2,1 nn lin kt phn cc manh, iu nay th hin trn
gian MO. Tham gia t hp co AO 1s cua nguyn t H va AO
2p
z
cua nguyn t F tao thanh MO lin kt co nng lng
thp hn nng lng cua cac AO. MO phan lin kt
8
co nng
lng cao hn nng lng cua cac AO. Nguyn t F con co
cac AO khng tham gia vao t hp la 2s (do chnh lch qua
nhiu v nng lng so vi 1s cua nguyn t H) va hai AO 2p
x
va 2p
y
(do khac tnh i xng). Nhng AO nay thc t vn
co nh hng ch tai nguyn t F va co nng lng nh
trong nguyn t nn c goi la cac AO khng lin kt. Gian
MO cua phn t HF va s phn b electron vao cac MO
c trnh trn hnh 3.10. Phn t HF co: N = 1, l = 0,92; E =
-565 kj/mol va = 1,83 D.
2.5. PHN CC CUA PHN T
2.5.1. Phn t phn cc va phn t khng phn cc
26
2p (A)
2p (B)

p

x

*
x

*
p

*
y

y
2s (A)
2s (B)
s

*
s
Hnh 2.10. Gian MO cua phn t
AB (chu k 2)
a. Phn t khng phn cc: la phn t trong o cac hat
nhn va cac my electron c phn b hoan toan i xng
cho trong tm in tch dng (cua
cac hat nhn) va trong tm in tch
m (cua cac my electron) hoan toan
trung vao nhau nh cac phn t N
2
, O
2
,
H
2
, CO
2
...
b. Phn t phn cc: la phn t trong o s phn b
cac hat nhn va my electron khng hoan toan i xng. Do
o cac trong tm in tch dng va m khng trung vao
nhau. V du cac phn t HCl, H
2
O...
2.5.2. Momen lng cc
Mi phn t phn cc la mt lng cc in gm 2
in tch im co tr tuyt i bng
nhau nhng ngc du nhau, t cach
nhau 1 khoang bng l.
Tch s: = l. c goi la momen
lng cc.
Momen lng cc c trng cho
phn cc cua phn t thng c
tnh ra n v Debye (k hiu D). 1 D =
0,333.10
- 30
C.m. Gia tr cua cac phn t
cng hoa tr thng nm trong khoang 0 - 4D, cua cac phn
t ion thng nm trong khoang 4 - 11D.
V du: Phn t: HCl HBr HI H
2
O SO
2
NH
3
(D): 1,04 0,79 0,38 1,86 1,61 1,46
2.5.3. S phn cc
a. S phn cc hoa phn t va ion
Di tac dung cua in trng ngoai (v du in trng
tao ra bi 2 ban cua 1 tu in) cac phn t va ion b bin
i cu truc va do o thay i tr s momen lng cc.
Hin tng o goi la s phn cc hoa phn t va ion.
b. S phn cc hoa hp cht
khng phn cc
Khi khng co in trng ngoai, phn
t cua hp cht co = 0. Khi phn t
nm trong in trng gia hai ban
cua tu in, cac hat nhn mang in
dng b hut v pha ban dng, do o
trong tm in tch dng va trong
tm in tch m b tach ra lam xut
hin mt momen lng cc ( 0).
Hin tng phn cc hoa nh vy
c goi la s phn cc hoa cam
ng hay phn cc hoa bin dang.
ln cua momen lng cc cam ng t l vi in
trng tac dung:
c
= E, trong o E la cng in
27
H
+
Cl
-
H
+
H
+
O
-
+
-
+
+
+
+
+
-
-
-
-
-
Hnh 2.12. Hin
tng phn cc
hoa bin dang
+ -
+ -
l
Hnh 2.11. Lng cc
phn t
trng, la phn cc hoa cam ng phu thuc vao cu
tao phn t cua mi cht.
c. S phn cc hoa i vi hp cht khng phn
cc
Khi cho cac phn t phn cc vao in trng gia hai tu
in th:
+ Cac lng cc phn t trc kia do chuyn ng nhit
nn sp xp hn n by gi do anh hng cua in
trng nn phn nao co s u tin nh hng theo phng
cua in trng. o la s phn cc hoa nh hng.
+ Do anh hng cua in trng ngoai mi lng cc
phn t b keo dai ra lam tng tr s cua momen lng cc.
o la s phn cc bin dang.
d.
S
phn cc hoa tng h gia cac ion
Khi cac ion lai gn nhau in trng tao bi mt ion nay co
th gy ra s phn cc hoa i vi ion kia. o la s phn
cc hoa tng h gia cac ion. Hin tng nay lam tng
tnh cht cht cng hoa tr cua lin kt ion va lam tng
bn cua lin kt ion.
2.6. CAC MI LIN KT YU
2.6.1. Lin kt hiro
a. Khai nim: Xet phn t HF. V m in cua F rt ln
nn trong mi lin kt H - F my electron lin kt b hut lch
manh v pha nguyn t F lam cho nguyn t F tch in m,
nguyn t H ch con lai gn nh tr troi hat nhn mang in
dng nn co th n kha gn nguyn t F va chui vao bn
trong vo electron cua nguyn t F cua phn t HF khac va hnh
thanh mi lin kt mi nguyn t F nay: H
+
- F
_
..... H
+
- F
_
.
Mi lin kt mi hnh thanh nay c goi la lin kt hiro.
Do s tao thanh lin kt hiro nn cac phn t HF lin hp
lai vi nhau thanh nhng phn t lin hp dang (HF)
n
vi n =
2 khi trong dung dch nc va n = 4 khi th kh.
b. bn lin kt hiro: Lin kt hiro cang bn khi:
nguyn t phi kim lin kt (bng hoa tr chnh) vi H co
m in cang ln va kch thc cang nho, nguyn t phi kim
tham gia lin kt hiro co m in cang ln va kch thc
28
Hnh 2.13. Hin tng phn
cc hoa nh hng
cang nho. Lin kt hiro co nng lng vao c 840 kJ/mol (hay
210 kcal/mol)
c. Anh hng cua lin kt hiro n tnh cht cua cac
cht: Lin kt hiro gy ra hin tng lin hp phn t, lam
tng nhit nong chay, nhit si, tng nhit hoa hi,
nhit dung; gy ra s bin i bt thng khi lng
ring cua nc. Lam giam in li cua axit va anh hng
n s hoa tan ln nhau gia cac cht long.
2.6.2. Lc Vander - Waals
Thc nghim cho bit gia cac phn t (k ca phn cc
va khng phn cc) lun lun co lc tng tac hut va y.
Cac loai lc hut gm tng tac khuych tan (gi vai tro
chnh trong tt ca cac trng hp tng tac gia cac phn
t) va tng tac nh hng (gi vai tro quan trong khi phn
t phn cc manh con tng tac cam ng noi chung khng
quan trong). Ngoai lc hut gia cac phn t con co lc
y. Khi cac phn t tin sat n gn nhau, cac my electron
bt u xen phu ln nhau th gia cac phn t bt u
xut hin lc y. Lc y tng nhanh khi giam khoang
cach gia tm cua hai phn t.
Nng lng tng tac toan phn gia hai phn t la tng
nng lng hut va nng lng y. Tng tac nay co tr s
cc ai ng vi khoang cach cn bng r
0
gia tm cua hai
phn t tham gia tng tac va c goi la lc Vander -
Waals. Nng lng tng tac Vander - Waals tng i nho
(<40 kJ/mol) va giam nhanh khi kch thc phn t , khi
lng phn t va khoang cach gia cac phn t tng ln.
Lc Vander - Waals khng co tnh chon loc va khng co tnh
bao hoa.
2.7. TRANG THAI TP HP CUA CAC CHT
mt iu kin xac nh, mt cht co th tn tai
trang thai kh, long hoc rn thuy theo quan h so sanh cua
hai yu t sau:
+ Chuyn ng nhit cua cac hat: lam cho cac hat phn
b hn n va co khuynh hng chim toan b th tch
khng gian cua cua bnh cha. Yu t nay c anh gia
bng ng nng chuyn ng cua hat.
+ Lc hut cua cac hat: lin kt cac hat lai thanh nhng
tp hp cht che co cu truc xac nh. Yu t nay c
anh gia bng th nng tng tac gia cac hat.
2.7.1. Trang thai kh
ng nng chuyn ng nhit vt xa th nng tng tac
gia cac hat v vy cac hat (phn t kh) co th chuyn
ng gn nh t do chim toan b th tch cua bnh
cha, cac phn t kh ch co th va cham an hi vi nhau
va vi thanh bnh. Mi trang thai cua cht kh c c
trng bng mt b cac thng s trang thai: nhit (T),
29
ap sut (P), th tch (V), s mol (n), khi lng (m)... ng
nng trung bnh cua phn t kh c tnh theo cng thc:
kT .
2
3
2
v . M
2
.
i vi kh ly tng (khng co th tch ring va khng co
lc hut gia cac phn t kh) ta co phng trnh:
RT
M
m
nRT PV

Tuy nhin, i vi kh thc ta phai tnh n th tch ring
cua cac phn t kh va lc hut gia cac phn t kh.
Phng trnh trang thai cho kh thc se la:
( ) RT ) b V
V
a
P
2

,
_
+
,
Trong o a, b la nhng hng s phu thuc vao tng cht
kh.
3.7.2. Trang thai long
S khac nhau gia ng nng chuyn ng nhit cua
phn t va th nng tng tac gia chung khng ln do o
phn t cht long vn co cac chuyn ng quay, dao ng
va tnh tin nhng khng th thoat khoi vung tac dung cua
lc Vander - Waals (c 10A
0
). V vy, cht long co th tch
xac nh nhng khng co hnh dang xac nh.
3.7.3. Trang thai rn
Th nng tng tac gia cac hat ln hn hn ng nng
chuyn ng nhit cua cac hat, do o cac hat c sp
xp thanh nhng cu truc xac nh, mi hat nhn hu nh
khng con kha nng chuyn ng tnh tin ma ch co kha
nng dao ng quanh v tr cn bng.
a. Cht v nh hnh: Trong cht v nh hnh cac phn t
sp xp hn n, v vy cht v nh hnh c coi la
cht long qua lanh, co tnh ng hng. Cht v nh hnh
khng th t kt tinh thanh tinh th co hnh dang xac
nh , khng co nhit nong chay xac nh.
b. Cht tinh th:
- Trong tinh th cac nguyn t, phn t, ion c sp xp
theo mt trt t xac nh. Trt t nay quyt nh hnh
dang va tnh i xng cua tinh th.
- Co kha nng t kt tinh thanh cac tinh th co hnh dang
va tnh i xng xac nh.
- Co nhit nong chay xac nh, khng i trong sut
qua trnh nong chay.
- Co tnh nh hng (con goi la tnh vect hay tnh bt
ng hng). o la s th hin tnh cht vt l, hoa hoc
theo nhng phng khac nhau mt cach khac nhau.
Da vao ban cht cac mi lin kt hoa hoc trong tinh
th ngi ta phn bit cac dang mang li phn t va
mang li ion. Trong mang li ion: cac nut li la do cac ion
dng hoc m ln lt chim gi, cac ion nay lin kt vi
nhau bng lin kt ion. bn cua mang li ion c
30
anh gia bng nng lng mang li. o la nng lng
c giai phong khi tao thanh 1 mol cht tinh th t cac ion
trang thai t do. V mt l thuyt co th tnh nng
lng mang li bng cng thc Born:
,
_

n
1 n
. a .
R
e Z
. N U
2 2
0
(3-10)
Trong o: N
0
la s Avogadro, e la in tch electron (tnh ra
culong), Z la in tch ion (ly
e
lam v), a la hng s
Madelung phu thuc vao dang cu truc, n la h s y
Born phu thuc vao dang cu tao vo electron cua nguyn
t.
T cng thc Born, Kapustinski a ra cng thc gn ung:
+
+
+
m
r r
Z . Z
1 , 256 U
(3-
11)
trong o: Z
+
, Z
-
la in tch ion (ly
e
lam n v).
r
+
, r
-
la ban knh cation va anion.

m
la tng s cac cation va anion trong cng thc
phn t cua hp cht ion.
c. Hin tng ng hnh va tnh a hnh
Hin tng ng hnh la hin tng nhng cht rn co
cng thc hoa hoc cung mt dang, co cung dang cu truc
mang li tinh th va co th thay th nhau trong mang li
tinh th tao thanh cac tinh th hn tap (nh KBr va KCl).
Hin tng a hnh la hin tngmt cht trong nhng
iu kin khac nhau (t
o
C, p) co th tn tai nhng dang
cu truc tinh th khac nhau (nh S dang n ta va dang ta
phng).
====================
PHN TH HAI
NHIT NG HOA
HOC
M u: mt s khai nim c
ban cua nhit ng hoc
Nhit ng hoc la khoa hoc nghin cu cac quy lut iu
khin trao i nng lng, c bit nhng quy lut co lin
31
quan ti cac bin i nhit nng thanh cac dang nng lng
khac.
1) H va mi trng
H nhit ng hay goi tt la h - la mt vt hay mt
nhom vt, gm mt s ln phn t, nguyn t (mt phn
cua vu tru) ly ra nghin cu, phn con lai goi la mi
trng. Gianh gii gia h va mi trng co th thc va
cung co th la tng tng.
H co trao i cht va nng lng vi mi trng goi la
h m. H ch trao i nng lng, khng trao i cht vi
mi trng goi la h kn. H c lp la h khng trao i
nng lng va cht vi mi trng.
2) Quy c v du trong qua trnh trao i nng
lng
Cng W va nhit lng Q u la nhng ai lng ai
s va c o bng cung mt n v. Trong nhit ng hoa
hoc, n v thng c dung o nhit lng la calo va
Jun (1 cal = 4,184 J).
Quy c v du trong qua trnh trao i nng lng di
dang bt k gia h va mi trng nh sau: h nhn nng
lng: du +; h nhng nng lng: du -.
3) Trang thai cua h va nhng thng s trang thai
Trang thai v m cua h c xac nh bng tp hp
cac tnh cht v m cua no co th o c trc tip hay
gian tip nh nhit , ap sut, th tch, khi lng,
thanh phn hoa hoc... Nhng ai lng nay c goi la
cac thng s trang thai. Nhng thuc tnh cua thng s
trang thai t l vi khi lng (th du th tch, khi
lng) c goi la thuc tnh dung lng; con nhit ,
ap sut, nng , nht... khng phu thuc vao khi
lng c goi la thuc tnh cng .
4) Bin i thun nghch va bin i bt thun
nghch
Mt h trang thai cn bng nhit ng khi gia tr cua
cac thng s trang thai moi im cua h phai nh nhau
va khng thay i theo thi gian. Trong trng hp nay tn
tai ng thi cn bng nhit, cn bng c va cn bng hoa
hoc. Khi mt h ang trang thai cn bng ma ta thay i
gia tr cua mt trong cac thng s trang thai th h se
thc hin mt s bin i va se at ti mt trang thai
cn bng ng vi cac gia tr mi cua cac thng s trang
thai.
Nu h chuyn t mt trang thai cn bng nay sang
mt trang thai cn bng khac v cung chm qua lin tip
cac trang thai cn bng th s bin i c goi la
thun nghch. Bin i thun nghch la mt trng hp l
tng, trong thc t khng thc hin c v mt s
bin i nh th se xay ra rt lu.
32
Chung ta coi nhng bin i thun nghch la nhng bin
i thc hin trong mt khoang thi gian xac nh, qua mt
day lin tip cac trang thai cn bng rt gn nhau. Ngc
lai la s bin i bt thun nghch. Nh vy, qua trnh
thun nghch la qua trnh cn bng con qua trnh bt thun
nghch la qua trnh khng cn bng, ngha la qua trnh t
xay ra.
5) Ham trang thai
Mt ham F (p,v,T...) c goi la mt ham trang thai nu
gia tr cua no ch phu thuc vao cac thng s trang thai
cua h ma khng phu thuc vao cach bin i cua h.
iu nay co ngha rng nu h chuyn t trang thai 1
(P
1
,V
1
,T
1
) sang trang thai 2 (P
2
,V
2
,T
2
) th F = F
2
- F
1
ch phu
thuc vao gia tr (P
1
,V
1
,T
1
) va (P
2
,V
2
,T
2
) ch khng phu thuc
vao tnh cht cua qua trnh bin i (thun nghch hay bt
thun nghch).
==========================
CHNG 3
NGUYN L I CUA NHIT NG
HOC-NHIT HOA HOC
3.1. NGUYN L I CUA NHIT NG HOC
3.1.1. Khai nim ni nng
Nng lng cua h gm 3 phn:ng nng chuyn ng
cua toan h + th nng cua h do h nm trong trng
ngoai + ni nng cua h.
Trong nhit ng hoa hoc thng khao sat h ng yn
va tac dung cua trng ngoai khng i, do o ta ch quan
tm ti ni nng cua no.
Ni nng cua h gm ng nng chuyn ng cua cac
phn t, nguyn t, hat nhn va electron (tnh tin, quay...)
va th nng tng tac (hut va y) cua cac phn t, nguyn
t, hat nhn va electron.
3.1.2. Phat biu nguyn l I cua nhit ng hoc
Nguyn l I cua nhit ng hoc thc cht la nh lut
bao toan va chuyn hoa nng lng: nng lng khng t
nhin sinh ra, khng t nhin mt i, no ch chuyn t dang
nay sang dang khac. No khng nh tnh bt dit cua nng
lng.
Gia s mt h kn trang thai1 (co ni nng U
1
) chuyn
sang trang thai 2 (co ni nng U
2
). Khi o no trao i vi mi
trng nhit nng Q va cng W. Nguyn l I khng nh nng
lng trao i nay co gia tr bng bin thin ni nng cua
h: U = U
2
- U
1
= W + Q = const
33
Do o co th phat biu nguyn l I nh sau: Tn tai mt
ham c trung cho trang thai cua h goi la ni nng, k
hiu la U va. dU la mt vi phn toan phn.
S bin i ni nng (U) cua h chuyn t trang thai 1
sang trang thai 2 bng tng s ai s cua tt ca cac nng
lng trao i vi mi trng trong qua trnh bin i nay.
i vi mt bin i v cung nho: dU = W + Q; i vi
mt bin hu han:
Q W dU U
2
1
+
. (dU: vi phn toan phn;

W va Q: khng phai la vi phn toan phn).
3.1.3. Nhit ng tch, nhit ng ap
Xet mt h ch trao i nhit va cng c hoc vi mi
trng.
Nhit ng tch: Nu bin i thc hin V = const th:
A = -pdV = 0
T dU = W + A dU = Q hay

const V
V
Q Q U

Q
V
la nhit ng tch, gia tr cua no ch phu thuc vao
trang thai u va cui cua h.
Nhit ng ap: Nu bin i xay ra P = const th U =
U
2
- U
1
= W + Q
P

ma
) V V ( P pdV W
1 2
2
1

U
2
-U
1
= Q
P
-P(V
2
- V
1
) hay: Q
P
= (U
2
+
PV
2
) - (U
1
+ PV
1
);
t: H = U + PVTa co: Q
P
= H
2
- H
1
= H; Q
P
goi la nhit
ng ap.
H c goi la entanpi, no la mt ham trang thai v: U va
PV u la ham trang thai.
Trng hp tng quat: H = U + PV + VP.
3.2. AP DUNG NGUYN L I CUA NHIT NG HOC - NHIT
HOA HOC
Hu ht cac phan ng hoa hoc xay ra u kem theo s
thu hay toa nhit. Nhit hoa hoc la khoa hoc nghin cu
hiu ng nhit cua cac qua trnh hoa hoc. Nhim vu cua
nhit hoa hoc la xac nh nhit dung cua cac h hoa -l, o
va xac nh nhit cua cac qua trnh hoa hoc cung nh s
phu thuc cua nhit vao nhit va thanh phn cua h.
C s cua nhit hoa hoc la hai nh lut Hess (1836) va
Kirchhoff (1859). V mt lch s, nh lut Hess tm ra trc
nguyn l I (1844) nhng v mt logic co th xem hai nh
lut trn la h qua cua nguyn l I.
3.2.1. Nhit cua phan ng
Xet qua trnh bin i 1 mol cht (h) t trang thai 1
sang trang thai 2: V = const th U = Q
V
, con P = const th
H = Q
P.
Q
V
va Q
P
c goi ln lt la nhit phan ng
34
ng tch va nhit phan ng ng ap va c goi la hiu
ng nhit cua phan ng (ch trong trng hp nay gia tr
cua chung mi ch phu thuc vao trang thai u va trang
thai cui).
K hiu
0
298
H biu th s bin i entanpi cua phan ng
xay ra ktc (tai 298Kva 1atm, cht tham gia va san phm
trang thai chun).
Gia nhit ng ap va nhit ng tch (phan ng gia
cac kh l tng) co mi lin h:
H = (U + pV)
P
= U + pV ; Q
P
= Q
V
+ nRT
Trong o: n = s mol san phm kh - s mol cht kh tham
gia phan ng.
3.2.2. nh lut Hess va h qua
nh lut Hess c phat biu nh sau: Hiu ng nhit
cua mt phan ng ch phu thuc vao trang thai u va
trang thai cui cua cac cht tham gia va cac cht tao thanh
ch khng phu thuc vao cac giai oan trung gian. Thut
ng hiu ng nhit phai hiu la nhit cua phan ng thc
hin ap sut (hoc th tch) khng i va h khng sinh
cng nao khac ngoai cng c hoc, ng thi qua trnh phan
ng la bt thun nghch.
Da vao cac h qua cua nh lut Hess co th tch c
hiu ng nhit cua cac phan ng.
a) H qua 1: Hiu ng nhit cua phan ng thun bng
hiu ng nhit cua phan
ng nghch nhng
ngc du.
H
t
+ H
n
= 0 H
t
= - H
n
b) H qua 2: Hiu ng nhit cua mt phan ng bng
tng nhit sinh cua cac cht cui tr i tng sinh nhit cua
cac cht u
Nhit sinh hay nhit tao thanh cua mt cht la nhit
lng thoat ra hay thu vao khi tao thanh mt mol cua cht
o t cac n cht bn vng iu kin o. T nh
ngha nay ta suy ra sinh nhit cua mt n cht bn iu
kin tiu chun bng khng:
0 ) ncht ( H
0
S , T

.

) thamgia ( H ) sanphm ( H H
s x
Xet phan ng: aA + bB cC + dD
Ta co: H
T
= [cH
T,s
(C) + dH
T,s
(D)] - [aH
T
,s(A) + bH
T,s
(B)]
c) H qua 3: Hiu ng nhit cua mt phan ng bng
tng nhit chay cua cac cht tham gia tr i tng nhit
chay cua cac cht tao thanh.
35
A
B
H
n
H
t
Nhit chay cua mt cht la nhit lng thoat ra khi t
chay hoan toan 1 mol cht o thanh cac oxit cao nht bn
iu kin o.
Ta co: H
T
= [aH
T,cs
(A) + bH
Tcs
(B)] - [cH
T
,c(C) + dH
T,c
(D)]
3.2.3. S phu thuc cua hiu ng nhit vao nhit
a. Nhit dung
Nhit dung (C) la nhit lng cn thit cn cung
cp cho h nhit cua h tng ln 1 iu kin
a cho va trong khoang nhit o khng xay ra s chuyn
pha. C la ham cua nhit va thng c biu din di
dang chui:
+ + ) 2 , 1 , 0 n ( T a T a T a a C
n
n
2
2 1 0
Nhit dung mol ng tch C
V
: la nhit lng cn
thit nng nhit cua 1 mol cht nguyn cht ln 1K
iu kin th tch khng i va trong khoang nhit o
khng xay ra s chuyn pha:
( )
,
_
2
1
T
T
V V
V
V
dT C U Q
T
U
C
Nhit dung mol ng ap C
P
: la nhit lng cn
thit nng nhit cua 1 mol cht nguyn cht ln 1 K
iu kin ap sut khng i va trong khoang nhit o
khng co s chuyn pha:
( )
,
_
2
1
T
T
P P
P
P
dT C H Q
T
H
C
;
n
n P
T a C
=>
+ +
2
2 1 0
n
n P
T a T a a T a C
Bit C
V
va C
P
co th tnh c s bin i ni nng U
va entanpi H theo nhit .
b. Nhit bin i trang thai: Nu P = const, mt cht
thay i trang thai (nong chay, ng c, bay hi, hoa long,
thng hoa, bin i a hnh) th trong qua trnh o nhit
se khng i nhng h a trao i nng lng vi mi
trng. Nhit lng trao i o c goi la nhit bin
i trang thai.
c. S phu thuc cua hiu ng nhit cua phan ng
vao nhit . nh lut Kirchhoff
Ta co:
+
2
1
1 2
T
T
n
n T T
dT T a H H
=>
) T / 1 T / 1 ( a ) T T ( a 2 / 1 ) T T ( a H H
1 2 2
2
1
2
2 1 1 2 0 T T
1 2
+ +
+ Nu bit hiu ng nhit cua phan ng mt nhit
nao o th du
0
298
H va nu bit phng trnh C
P
= (T) th
co th tnh c hiu ng nhit cua phan ng nhit
bt k nao.
+ Thng s bin i cua C
P
theo T khng nhiu do o
nu
1 H
0
298
>>
(th du i vi cac phan ng chay) va trong
36
khoang nhit khao sat khng co s chuyn pha th:
0
298
T
298
0
P
0
298
0
T
H dT C H H +
ngha la trong trng hp nay co

th coi H
0
= const.
+ Trong khoang T kha hep co th coi C
P
= const =>
) 298 T ( C H H
0
P
0
298
0
T
+
3.2.4. Nng lng lin kt va nhit cua phan ng
a. Nng lng lin kt
Nng lng lin kt cng hoa tr la nng lng thoat ra khi
tao thanh mt lin kt cng hoa tr t hai nguyn t t do
trang thai hi (tnh bng kJ.mol
-1
). Trong trng hp phn
t nhiu nguyn t, ngi ta tha nhn s bin i
entanpi cua phan ng tao thanh cac phn t nay trang
thai hi t cac nguyn t cua cac nguyn t trang thai hi
bng tng nng lng cua cac lin kt c tao thanh.
y la nng lng lin kt trung bnh.
b. Nhit phan ng va nng lng lin kt
Phan ng hoa hoc v ban cht la pha v cac lin kt ccu
va hnh thanh cac lin kt mi. Do o nu phan ng thc
hin ap sut khng i va nhit T th s bin i
entanpi cua phan ng chnh bng tng nng lng cua cac
lin kt c tao thanh tr i tng nng lng cua cac lin
kt b pha v. Vy, nu bit nng lng cac lin kt co
th tnh c nhit cua phan ng.
V du: Xac nh nng lng mang li tinh th cua NaCl
(r). Theo nh ngha nng lng mang li cua NaCl la nng
lng thoat ra khi tao thanh 1 mol tinh th NaCl t cac ion
Na
+
va Cl
-
trang kh. Nng lng nay khng th o c
bng thc nghim, nhng nhit cua cac qua trnh sau co
th o c:
Nhit nguyn t hoa Na(r): Na (r) Na (h) H
1
=
+108,724 J.mol
-1
.
Nhit phn li Cl
2
(k): Cl
2
(k) 2Cl (k) H
2
= +242,672
J.mol
-1
Nng lng ion hoa Na (h): Na (h) Na
+
(h) + e H
3
=
+489,528 J.mol
-1
Ai lc electron cua Cl (k): Cl (k) + e Cl
-
(k) H
4
=
-368,192 J.mol
-1
Nhit cua phan ng: Na (r) + 1/2 Cl
2
(k) NaCl (r) H
5
=
-414,216 J.mol
-1
xac nh nng lng mang li cua tinh th NaCl ta dung
chu trnh nhit ng Born - Haber sau:
Theo
nh
37
Na (r) + 1/2 Cl
2

(k)
NaCl(r)
Na (h) + Cl
(k)
Na
+
(h) + Cl
-

(k)
Trang
thai
u
u
Trang
thai
cui
cui
H
1
1/2H
2
H
3
H
4
H
5
x
=
lut Hess: H
5
= H
1
+ 1/2H
2
+ H
3
+ H
4
+ x x = - 765,672
J.mol
-1
.
=====================
CHNG 4:
NGUYN L 2,3 CUA NHIT NG HOC -
CAC HAM NHIT NG VA CHIU CUA
QUA TRNH HOA HOC
M u.
Trong t nhin, cac qua trnh l hoc va hoa hoc... xay ra
theo chiu hoan toan xac nh, v du: nhit t truyn t
vt nong sang vt lanh hn, Kh t chuyn t ni co ap
sut cao n ni co ap sut thp hn, hay Zn + 2HCl= ZnCl
2
+
H
2
. Cac qua trnh ngc lai khng th t
xay ra. Trong hoa hoc, vic bit nhng tiu chun cho phep
tin oan c chiu cua phan ng hoa hoc va gii han
t din bin cua chung (do o xac nh c hiu sut
cua phan ng) la iu rt quan trong.
Nguyn l 1 cho phep tnh nhit cua cac phan ng nhng
khng cho phep tin oan chiu va gii han cua qua trnh.
Nguyn l 2 cho phep giai quyt cac vn nay.
4.1. NGUYN L 2 CUA NHIT NG HOC - ENTROPI
giao trnh vt l (phn vt l phn t va nhit hoc) ta
thy co nhiu cach phat biu nguyn l 2, mi u tng
nh hoan toan khac nhau nhng thc t cac cach phat biu
la tng ng.
Trong hoa hoc, phat biu nguyn l 2 di dang ham trang
thai entropi la thun li nht.
4.1.1. Nguyn l 2 cua nhit ng hoc
Phat biu Tn tai mt ham c trng cho trang thai cu
h goi la entropi, k hiu la S. dS la mt vi phn toan phn.
Gia s co mt bin i thun nghch v cung nho, trong
o h trao i vi mi trng nhit T mt lng
nhit lng Q
tn
, s bin i entropi trong qua trnh nay
c xac nh bi:
T
Q
dS
tn
. Nh vy, n v cua entropi la

J.K
-1
, cal.K
-1
.
y la biu thc toan hoc cua nguyn l 2.
Du = qua trnh thun nghch (cn bng)
(4-1)
Du > qua trnh bt thun nghch (t xay ra)
38
2
1
T
Q
S
T
Q
dS
Ghi chu: S la mt ham trang thai do o S ch phu thuc
vao trang thai u va trang thai cui, ngha la:

>

2
1
2
1
,
T
Q
S S
T
Q
S S
btn
tn btn
tn
btn tn
. T o ta thy Q
tn
> Q
btn
xac nh s bin i entropi cua qua trnh bt thun
nghch trc ht ta hnh dung mt qua trnh bt thun
nghch co cung trang thai u va trang thai cui vi qua
tnh bt thun nghch sau o tnh S theo:

2
1
T
Q
S
tn
4.1.2. Ap dung nguyn l 2 vao trng hp h c lp
i vi h c lp:Trong qua trnh thun nghch (cn bng),
entropi cua h la khng i. Trong qua trnh bt thun
nghch ngha la t xay ra, entropi cua h tng. T

2
1
T
Q
S
tn

nn Q
tn
= 0 S = 0; Q
btn
>0 S > 0. iu nay co ngha rng
trong cac h c lp, entropi cua h tng cho ti khi at gia tr
cc ai va h at ti trang thai cn bng. ao lai ta co
th noi:
Trong h c lp: Nu dS > 0 (S) H t din
bin.
Nu dS = 0 d
2
S < 0 S = S
max
H trang
thai cn bng
4.1.3. S bin i entropi trong qua trnh dan n
ng nhit cua kh l tng
Xet s gian n ng nhit cua 1 mol kh l tng, i vi
qua trnh ng nhit (T = const):
1
2
1
2
ln
ln
V
V
R
TV
V RT
T
Q
S
tn

. V V
2
> V
1
nn S > 0, ngha la qua
trnh t xay ra. (4-2)
V ap sut t l nghch vi th tch nn iu nay cung co
ngha rng kh t chuyn t ni co ap sut cao sang ni co
ap sut thp hn.
4.4.4. S bin i entropi trong qua trnh thay i
trang thai cua cht nguyn cht
Trong qua trnh bin i trang thai cua mt cht nguyn
cht, nhit la khng i. Do o, s bin i entropi cua
mt mol cht nguyn cht trong qua trnh bin i trang
thai xay ra ap sut khng i se la:
T
H
S

, trong o:T la
nhit va H la nhit bin i trang thai.
4.1.5. S phu thuc cua entropi cua cht nguyn
cht vao nhit
Ta hay tnh s bin i entropi cua mt cht nguyn
cht khi nhit thay i va trong khoang nhit khao
sat, cht o khng thay i trang thai.
39
+ nu qua trnh xay ra p= const th:
1
2
2
1
ln
T
T
C
T
dT
C S
P P

.
(4-4)
+ Nu s bin i xay ra v = const th:
1
2
ln
T
T
C S
V

(4-5)
4.1.6. S bin i entropi trong cac phan ng hoa
hoc
Ta hay tnh s bin i entropi cua phan ng (thc hin
ap sut khng i):
nA + mB pC + qD
V entropi la mt ham trang thai va ai lng dung nn:
S
T
= [pS
T
(C) + qS
T
(D)] -[[nS
T
(A) + mS
T
(B)]

) thamgia ( S ) sanphm ( S S
T T T
(4-6)
Nu phan ng thc hin iu kin chun va 298
0
K
th:

) thamgia ( S ) sanphm ( S S
0
298
0
298
0
298
4.1.7. Y ngha thng k cua entropi
Mt h c lp co khuynh hng t din bin n trang
thai co xac sut nhit ng (k hiu la ) ln nht, ngha
la trang thai v m tng ng vi s trang thai vi m ln
nht. Boltzmann a chng minh c rng: S = kln. (k la
hng s boltzman). T o co th coi entropi la thc o
mc hn loan cua h.
4.2. NGUYN L 3 CUA NHIT NG HOC
4.2.1. Phat biu nguyn l 3: Cu truc l tng ma ta a
khao sat phn cu tao cht ch co th co i vi nhng
tinh th hoan hao khng tuyt i. Khi o, ng vi
mt trang thai v m ch co mt trang thai vi m do o theo
h thc Boltzmann: S = kln v = 1. Xut phat t o,
Nernst a ra nguyn l 3: Entropi cua cac cht nguyn cht
di dang tinh th hoan hao khng tuyt i bng 0.
S 0 (T 0)
4.2.2. Entropi tuyt i
Nguyn l 3 cho phep tnh entropi tuyt i cua cac cht
nguyn cht bt k nhit nao. Gia s ta nng 1 mol cua
cht nguyn cht dang tinh th hoan hao t 0
0
K ln nhit
T di ap sut khng i.
0
0
K T
nc

T
s
T
(nong chay) (si)
S bin i entropi trong qua trnh nay se la: S = S
t
- S
0
0
0
K entropi cua cht nguyn cht di dang tinh th
hoan hao S
0
= 0, do o:
40
dT
T
) hi ( C
T
H
dT
T
) long ( C
T
H
dT
T
) rn ( C
S
T
T
P
S
S
T
T
P
nc
nc
T
0
P
T
S
s
nc
nc

+
+ +
+
(4-7)
S
T
c goi la entropi tuyt i cua cht nguyn cht
nhit T va di ap sut P.
4.3. HAM NHIT NG, TIU CHUN T DIN BIN, GII
HAN CUA QUA TRNH 4.3.1. Cac ham th nhit ng
Trong c hoc, ta a gp khai nim th nng: Khi chuyn t
trang thai 1 sang trang thai 2, vt a thc hin mt cng
W va W = E
2
- E
1
= mg(h
2
- h
1
). Cng nay, nh a bit, khng
phu thuc vao cach chuyn vt t trang thai 1 sang trang
thai 2. Nh vy, th nng la mt ham trang thai, no la mt
ham th.
Tng t , ngi ta nh ngha th nhit ng nh
sau:Th nhit ng la nhng ham trang thai cua h ma
mt trong nhng tnh cht cua no la giam cua no trong
iu kin xac nh th bng cng do h thc hin trong
qua trnh thun nghch xay ra trong cac iu kin o
Gia s h trao i vi mi trng nhit T mt
lng nhit v cung nho Q va ngoai cng dan n v cung
nho W = -pdV, h con thc hin cng hu ch W (v du
cng in trong cac pin), theo nguyn l 1 ta co: dU = Q - pdV +
W; theo nguyn l 2:
T
Q
dS

Phi hp hai nguyn l 1 va 2 ta co: dU TdS - pdV + W

(4-8)
i vi qua trnh bin i thun nghch: dU + pdV - TdS =
W
max
(4-9)
+ Nu V = const va S = const th: (dU)
V,S
= W
max
U
V,S
=
W
max
(4-10)
+ Nu p = const va S = const th: d(U + pV)
p,S
= (dH)
p,S
=
W
max
=> H
p,S
= W
max
+ Nu V = const va T = const th: d(U - TS)
V,T
= W
max
t: A = U - TS. Ta co: dA
V,T
= W
max
A
V,T
= W
max

(4-11)
Ham A c goi la th ng nhit ng tch (goi tt la
th ng tch), nng lng Helmhotz.
+ Nu p = const va T = const th:d(U + pV - TS)
p,S
= W
max

d(H - TS)
p,T
= W
max
t: G = H - TS Ta co: dG
p,T
= W
max
G
p,T
= W
max
(4-12)
Ham G thng c goi la th ng nhit ng ap (goi
tt la th ng ap), nng lng Gibbs (do Gibbs a ra ln
u tin), entanpi t do.
41
Nh vy, theo nh ngha trn, ni nng U, entanpi H, ham
G = H - TS la nhng ham th nhit ng. Trong thc t
thng gp cac bin i ng ap, ng nhit nn ham
nhit ng G c s dung c bit rng rai.
4.3.2. Th nhit ng va tiu chun t din bin
va gii han cua qua trnh
Ta co: dU TdS - pdV + W
Ma G = H - TS nn dG = dH - SdT - TdS
H = U + pV nn dH = (U + pV) = dU + pdV + Vdp
=>
' W Vdp SdT dG + +
. y la phng trnh c
ban cua nhit ng hoc. (4-13)
Trong nhng h nhit va ap sut khng i, ch
nhng qua trnh nao kem theo s giam nng lng Gibbs
mi co th t xay ra va khi ham G at gia tr cc tiu: dG
= 0, d
2
G > 0 th h se at trang thai cn bng.
4.3.3. S bin i entanpi t do cua cac phan ng
hoa hoc
G la mt ham trang thai, do o s bin i entanpi t
do cua phan ng se bng tng entanpi t do cua cac cht
san phm tr i tng entanpi t do cua cac cht tham gia,
ng thi gia tr cua no phu thuc vao trang thai l hoc
cua cac cht, nhit va ap sut.
Ta co: G
T
= [cG
T,s
(C) + dG
T,s
(D)] - [aG
T
,s(A) + bG
T,s
(B)]
Entanpi t do chun tao thanh cua mt cht nhit
T la s bin i entanpi t do cua phan ng tao thanh 1
mol cht o t cac n cht bn iu kin chun (p =
101,325 kPa) va nhit T, k hiu la
0
,s T
G
. Entanpi t do
chun tao thanh cua cac n cht bng 0.
S bin i cua entanpi t do theo nhit
Ta co: G = H-TS ma
S
T
G
P

,
_
nn
P
T
G
T H G
,
_
+
Hay:
( )
P
T
G
T H G

,
_

+
2
P
T
H
T
T
G

,
_
,
_
va
2
P
T
H
T
T
G
,
_
,
_
(4-14)
Tch phn (4-14) se tm c s phu thuc cua G
T
vao
nhit
S phu thuc cua entanpi t do vao ap sut
T
S
T
G
P

,
_
. =>

2
1
) ( ) (
1 2
2
1
p
p
T T
Vdp p G p G dG
i vi kh l tng th:
kh) mol 1 vi i (
p
RT
V
42
Va:

+
2
1
p
p
1 T 2 T
p
dp
RT ) p ( G ) p ( G

1
2
1 T 2 T
P
P
ln RT ) p ( G ) p ( G +
(4-15)
Thng ta quan tm n s bin i cua ham G t trang
thai chun (G
0
) ngha la khi ap sut bin i t p
1
(= p
0
) = 1
atm = 760 mmHg = 101,325 kPa = 1,01325.10
5
n/m
2
.
Khi o:
0
2 0
T 2 T
P
P
ln RT G ) p ( G + . cho n gian, ta t P
2
/P
0
= p
(la mt h s, no cho bit ap sut phng phap ln hn ap
sut chun bao nhiu ln) th G
T
= G
0
T
+ RTlnp.
S bin i entanpi t dovao thanh phn cua
h - Khai nim th hoa hoc.
Gia s trong h co n
1,
n
2
, ...n
i
mol cht A1, A2, A
i
..., Khi o: G
= G(p,T,n
1
,n
2
,...,n
i
)
=> i
n n : p , T
i
1
n n : p , T
1 N , p N , T
dn
n
G
... dn
n
G
dT
T
G
dp
P
G
dG
i j i j

,
_
+ +
,
_
+
,
_
+
,
_
(4-16)
T:
V
n
G
N , T
i

,
_
,
S
T
G
N , p

,
_
va t i i
n n ; p , T
i
G
n
G
i j

,
_
Ta co:
+ +
i i
dn Vdp SdT dG
(4-17)
y la phng trnh c ban va tng quat cua nhit ng
hoa hoc. ai lng
I
c goi la th hoa cua cht i, Nh
vy: Th hoa cua mt cht la th ng ap mol ring phn
cua cht o trong hn hp (G
i
), no la tng kha nng sinh
cng hu ch (tnh cho 1 mol) cua h khi thm mt lng v
cung nho cht o vao h nhit , ap sut va s mol
cua tt ca cac cht khac khng i. Th hoa la mt ai
lng cng :

=
0
(T) + RTlnp (4-18)
T cng thc (5-26) thy rng nhit va ap sut
khng i, tiu chun t din bin va gii han cua qua
trnh hoa hoc va chuyn pha:
0 dn
i i

(4-19)
iu o co ngha rng tiu chun t din bin cua cac
qua tnh hoa hoc va chuyn pha la tng th cua cac san
phm phai nho hn tng th hoa cua cac cht ban u va
khi hai tng nay bng nhau th h se at cn bng.
4.3.4. Mi lin h gia cu tao va chiu cua phan
ng
ap sut va nhit khng i, mt phan ng se t
din bin khi: G = H - TS < 0
Du cua G do du va ln cua H va S se quyt nh.
Bang sau cho thy s phu thuc nay va cac kt lun v
kha nng t din bin va iu kin cua phan ng.
STT
H S G = H - TS
Kt lun
1 - +
G < 0
T xay ra
2 + -
G > 0
Khng t xay ra
43
3 - -
G co th < 0 khi T
thp
T xay ra T
thp
4 + +
G co th < 0 khi T cao
T xay ra T
cao
Gia H va S cua phan ng va cu tao nh a bit co
s lin h:
H = bn cua cac lin kt cui - bn cua cac lin
kt u.
S = hn loan cui - hn loan u.
========================
44
PHN TH BA
NG HOA HOC
VA CN BNG HOA
HOC
CHNG 06:
NG HOA HOC
ng hoa hoc la nganh khoa hoc nghin cu vn tc va
cac yu t anh hng ti vn tc cua cac phan ng cung
nh cua cac giai oan trung gian chuyn cac cht ban
u thanh cac san phm cui.
5.1. VN TC PHAN NG
c trng cho nhanh, chm cua cac phan ng,
ngi ta a ra khai nim vn tc cua phan ng. Vn tc
cua mt phan ng thng c o bng bin thin nng
cua mt trong cac cht tham gia hoc tao thanh trong
mt n v thi gian (n v cua vn tc phan ng la mol.l
-
1
.thi gian
-1
).
Gia s trong khoang thi gian t = t
2
- t
1
, nng cua mt
cht nao o bin thin mt lng la C = C
2
- C
1
th vn
tc trung bnh cua phan ng se la:
t
C
v
t
(5 -1)
Nu xet trong mt khoang thi gian dt v cung nho th vn
tc tc thi cua phan ng se la:
dt
dc
t
C
v
t
t
t

lim
0
(5 -2)
V vn tc phan ng la lun lun dng nn du + ng
vi vic xac nh vn tc cua phan ng theo bin thin
nng cht tao thanh con du - ng vi cht tham gia.
Trong nhiu trng hp, cac cht tham gia trong phng
trnh phan ng vi h s t lng khac nhau. V du: aA +
bB pC + qD
Khi o:
dt
dC
q
a
dt
dC
p
a
dt
dC
b
a
dt
dC
v
D C B A

(5-3)
Vn tc cua phan ng ngoai s phu thuc vao ban
cht cua cac cht tham gia con phu thuc vao nng cua
chung, nhit , s co mt cua cht xuc tac va nu xay
ra trong dung dch con phu thuc vao ban cht cua dung mi.
45
5.2. CAC YU T ANH HNG N VN TOC PHAN NG
5.2.1. Anh hng nng
a. i vi phan ng ng th: Nm 1864, Guldbert va
Waage (C.Gudlbert va P.Waage ngi Nauy) a ra mt nh
c goi la nh lut tac dung khi lng. Theo nh lut
nay: vn tc cua phan ng t l thun vi tch s nng
cac cht tham gia vi s mu lacac h s hp thc
i vi phan ng: aA + bB san phm th v = k[A]
n
[B]
m

(5 -4)
Trong o: [A] va [B] la nng mol.l
-1
cua cht A va cht B
thi im khao sat.
n, m: la s nguyn va n a, m b; trong mt s
trng hp th n = a, m =b. Gia tr cua n, m c xac nh
bng thc nghim. Tng (n + m) c goi la bc cua
phan ng. Con m va n ln lt la bc theo A va B, chung co
th nguyn hoc la phn s.
K c goi la hng s vn tc, phu thuc vao
ban cht cua cac cht tham gia va vao nhit . i vi
mt phan ng a cho va nhit khng i, no la mt
hng s.
Nu [A] = [B] = 1mol.l
-1
th v = k. Vy, hng s vn tc v
gia tr bng vn tc cua phan ng khi nng cac cht
bng 1 mol.l
-1
. Do o, no con c goi la vn tc ring cua
phan ng.
Phng trnh (6-4) biu din s phu thuc cua vn tc
phan ng vao nng cac cht co anh hng ln vn tc
c goi la phng trnh ng hoc cua phan ng. No
c xac nh bng thc nghim va la phng trnh c ban
cua ng hoc hnh thc.
b. i vi phan ng d th: Xet phan ng d th gia
cht kh va cht rn
C
gr
+ O
2
(k) CO
2
(k)
Do nng cua cht rn bng 1 nn ta co: v = k[O
2
].
Ngha la: trong trng hp co cht rn tham gia th nng
cua no khng co mt trong biu thc toan hoc cua nh
lut tac dung khi lng.
c. Bc cua phan ng, phn t s va c ch phan
ng
Da vao gia tr cua tng (n + m ) = 0,1,2,3; ngi ta phn
loai bc cua phan ng thanh phan ng bc 0,1,2,3.
S cac phn t tham gia vao mt giai oan c ban c
goi la phn t s cua phan ng. Nu giai oan c ban
cua phan ng ch co mt phn t tham gia th o la phan
ng n phn t (cac phan ng ng phn hoa, phan ng
phn li). Nu giai oan c ban, co hai phn t tham gia phan
ng th goi la phan ng hai phn t. Phan ng ba phn t
him hn.
5.2.2. Anh hng cua nhit
46
a. Quy tc Vant Hoff: Thc nghim cho thy khi nhit
tng ln th vn tc cua phan ng tng rt nhanh va c tng
ln 10
0
C th vn tc cua phan ng tng ln t 2 n 4 ln.
S ch vn tc cua phan ng tng ln bao nhiu ln khi
nhit tng ln 10
0
C goi la h s nhit va k hiu la
va ta co:

+
T
T
v
v
10
. y la biu thc cua quy tc kinh
nghim Vant Hoff. No ch ung trong khoang nhit khng
cao. Nu nhit T
1
vn tc cua phan ng la v
1
va
nhit T
2
vn tc cua phan ng la v
2
th:
1
10
2
.
1 2
v v
T T

(5-5)
b. Phng trnh Arrheniust
Quy tc kinh nghim cua Vant Hoff ch la s gn ung, t
co gia tr khoa hoc. Thc t hng cua nhit ti vn
tc cua phan ng dang phc tap hn nhiu. ng cong
thc nghim trn hnh 5.1 la dang iu tng quat cua anh
hng cua nhit ln vn tc phan ng. No co dang
iu cua ham luy tha. Nu biu din logarit cua hng s
vn tc k theo nghch ao nhit T th ta se c mt
ham bc nht co dang:
C
T
A
k ln ln +
(5 - 6)
2
ln
T
A
dT
k d

(5 -7)
Gia tr cua A co th xac nh theo th lnk - 1/T vi tg = A
hoc bng cach tnh tch phn phng trnh (5 -7). Trong
khoang nhit rt hep, thc nghim cho thy A rt t
bin i va co th coi A = const. Phn li bin va tch phn (5-
6) ta c:
1
]
1

1 2 1
2
1 1
ln
T T
A
k
k
(5 -8)
Bng cach xac nh hng s vn tc cua phan ng hai
nhit khac nhau, t (5-8) ta tnh c gia tr cua A. Thay
gia tr cua A vao (5-6) ta tnh c gia tr cua C. Va n y
co th tm c biu thc cua s phu thuc cua hng
s vn tc vao nhit .
5.2.3. Anh hng cua cht xuc tac
Cht lam bin i vn tc cua phan ng nhng no khng
co mt trong san phm cui cung cua phan ng c goi
47
v
T
lnk
1/T
o
o
o
o
o
o
o
1

2
o
o
o

o
o

o
o
Hnh 5.1: s bin
i cua vn tc phan
ng theo nhit .
Hnh 5.2: s bin i cua
logarit cua hng s vn tc
phan ng theo nghch ao nhit
.
la cht xuc tac. Hin tng lam bin i vn tc cua
phan ng di tac dung cua cht xuc tac goi la s xuc
tac.
Cht xuc tac lam tng vn tc cua phan ng goi la cht
xuc tac thun hay cht xuc tac dng, hay n gian ch la
cht xuc tac. Cht xuc tac lam giam vn tc cua phan ng
goi la cht xuc tac nghch, la cht xuc tac m hay la cht
c ch.
Nu cht xuc tac va cac cht tham gia phan ng cung
mt pha th goi la s xuc tac ng th. (V du, phan ng
gia SO
2
va O
2
co cht xuc tac la kh NO). Nu cht xuc tac
va cac cht tham gia phan ng cac pha khac nhau th goi
la s xuc tac d th. (V du phan ng tng hp amnic
t N
2
va H
2
dung bt st lam xuc tac).
Hin tng xuc tac di tac dung cua cac men c
goi la s xuc tac men. Nhiu prtin (nhng phn t cu
tao t amin axit va co cu truc khng gian xac nh cua
mach polypeptit) la nhng cht xuc tac cc k tt cho mt
s ln cac phan ng trong c th ng vt va c goi la
cac men (cac enzym)
Nhng cht, du ch vi mt lng rt nho, cung lam
giam manh tnh cht hoat ng cua cht xuc tac hoc co
th lam ngng hoan toan tac dung cua cht xuc tac c
goi la cht c xuc tac. Ngc lai, co nhng cht ch
cn thm mt lng nho cua chung vao cht xuc tac se
lam tng manh tnh hoat ng, tnh chon loc, tnh bn cua
cht xuc tac - nhng cht nh th c goi la cht kch
thch xuc tac.
Quy lut va c ch xuc tac: cht xuc tac co tac dung
chon loc cao - ngha la mt cht xuc tac co th xuc tac cho
phan ng nay nhng cha chc a la xuc tac cho phan ng
khac.
Hin nay, co nhiu thuyt v c ch tac dung cua xuc
tac. Cac thuyt nay tuy khac nhau nhng u thng nht
mt im la trong qua trnh phan ng, cac cht tham gia
tng tac vi cht xuc tac chuyn thanh trang thai trung
gian khng bn. C ch cua cht xuc tac ng th thng
c giai thch bng thuyt hp cht trung gian, con vi
xuc tac d th thng c giai thch bng thuyt hp
phu.
5.3. CAC PHAN NG PHC TAP
trn ta a khao sat nhng phan ng xay ra theo mt giai
oan va bc cua phan ng chnh bng phn t s cua giai
oan c ban o. Trong thc t, thng mt phan ng
khng phai la kt qua cua mt giai oan tng tac ma gm
nhiu giai oan. Nhng phan ng nh th c goi la
48
phan ng phc tap. Trong cac phan ng nay, ph bin
nht la cac phan ng song song, ni tip va thun nghch.
Phan ng nitro hoa bromobenzen bng axit nitric la mt
phan ng song song in hnh.
Trong cac phan ng ni tip, san phm cua giai oan trc
la cht u cua giai oan sau:
Trong thc t ta con gp cac phan ng dy chuyn (phan
ng chui). o la cac phan ng trong o kha nng xay ra
mi mt giai oan c ban gn lin vi s kt thuc co kt
qua cua giai oan c ban trc o va tip tuc nh th giai
oan c ban sau lai tao kha nng cho giai oan c ban sau
o. o la cac phan ng phn ra hat nhn cua cac nguyn t
phong xa.
=======================
49
A A
1
A
2
...
k
1
k
2
Br
+ HNO
3
H
2
SO
4
(
)
Br
NO
2
Br
NO
2
Br
NO
2
k
1
k
2
k
3
CHNG 6
CN BNG HOA HOC
Trong chng nay chung ta tm gii han t din bin cua
cac phan ng hoa hoc va t o tnh c nng cua
cac cht luc cn bng, tm ra cac yu t v anh hng
n s chuyn dch cn bng va nh vy tm c
nhng iu kin iu khin cac phan ng hoa hoc sao
cho at c hiu qua cao nht.
6.1. BIN THIN ENTANPI T DO TRONG QUA TRNH PHAN
NG
Chung ta bit rng moi phan ng u i ti trang thai
cn bng, o tn tai ng thi cht tham gia va san
phm cua phan ng nhng vi ty l khac nhau. Nu lng
san phm vt xa lng cht tham gia th phan ng o
c coi la phan ng mt chiu. Trong trng hp lng
san phm va lng cht tham gia khng khac nhau nhiu th
phan ng c coi la phan ng hai chiu hay con goi la
phan ng thun nghch.
Xet phan ng n gian nht: A B. Trong qua trnh phan
ng, thanh phn cua A va th hoa cua A giam dn con cua
B tng dn. Do o, dc cua ng cong G - se tng dn
ngha la ng cong G - se quay b lom xung di. Khi
A
=
B
th
0
,
,
_
P T
G
ngha la ham G at cc tiu va phan ng
at ti trang thai cn bng hoa hoc.
6.2. TRANG THAI CN BNG VA HNG S CN BNG
6.2.1. Phng trinh ng nhit Vant Hof - Hng s cn
bng
Xet phan ng gia cac kh l tng (thc hin nhit
va ap sut khng i):
aA + bB eE + dD
50
A

cb

B
A

cb

B
G
A

G
B
Goi p
A
, p
B
,

p
E
, p
ln lt la ap sut ring phn cua A, B, E, D

nhit T.
S bin i entanpi t do cua phan ng trn se la: G
T
=
(e
E
+ d
) - (a
A
+ b
B
)
Nhng:
i i i
p RTln
0
+ nn:
( ) ( ) [ ]
b
B
a
A
d
D
e
E
B A D E T
P P
P P
RT b a d e G
.
ln
0 0 0 0
+ + +
.
Vy, ta co:
b
B
a
A
d
D
e
E
T T
P P
P P
RT G G
.
ln
0
+
(6 -1)
Khi phan ng at ti cn bng th G
T
= 0, do o:
cb
b
B
a
A
d
D
e
E
T
P P
P P
RT G

,
_

.
ln
0
(6 -2) V i vi mt cht, ) (
0
T
i
ch phu thuc va nhit nn i vi mt phan ng a

cho const G
T

0
mi nhit xac nh.
Nh vy, i vi mt phan ng a cho, T = const, t s:
const K
P P
P P
P
cb
b
B
a
A
d
D
e
E

,
_
.
(6 -3) K
P
c goi la hng s cn bng,
i vi mt phan ng a cho, no ch phu thuc vao nhit
. K
P
cang ln th phan ng tin hanh theo chiu thun
cang manh va ngc lai.
Thay (6 -3) vao (6 -2) ta c: G
0
T
= - RT lnK
P

(6 -4)
Thay ( 6-4) vao (6 -1) ta co:
,
_

b
B
a
A
d
D
e
E
P T
P P
P P
K RT G
.
ln ln
(6 -5)
y la phng trnh ng nhit Vant Hoff.
Ngoai hng s cn bng K
P
ra trong thc t con s
dung cac hng s cn bng K
C
, K
N
, K
n
. Goi V la th tch cua
h, C
i
la s mol cht i co trong mt n v th tch. Nu V
tnh bng lt th C
i
c goi la nng mol.l
-1
cua kh i. ta
co:
p
i
V = n
i
RT
RT C RT
V
n
p
i
i
i

( )
( ) ( ) [ ] b a d e
cb
b
B
a
A
d
D
e
E
P
RT
C C
C C
K
+ +
,
_
.
(6 -6)
t
cb
b
B
a
A
d
D
e
E
C C
C C
,
_
C
K
va n = (e + d) - (a + b) => K
P
= K
C
(RT)
n
va K
P
= K
N
.P
n
Hng s cn bng K
C
phu thuc vao ban cht cua cac
cht tham gia va vao nhit . i vi mt phan ng cho
sn no ch phu thuc vao nhit .
Hng s cn bng K
N
va K
n
ngoai s phu thuc vao
ban cht cua cac cht tham gia va nhit con phu thuc
vao ap sut chung cua hn hp luc cn bng. Ring hng
51
s cn bng K
n
con phu thuc vao ca thanh phn ban u.
Khi tng s phn t kh cua hai v bng nhau (n = 0) th K
P
= K
C
= K
N
= K
n
. Trong trng hp nay, i vi mt phan ng
a cho, cac hng s cn bng ch phu thuc vao nhit .
T phng trnh hng s cn bng ta rut ra kt lun:
nhit khng i, khi phan ng at ti cn bng, ap sut
ring phn va nng cua cac cht khng thay i.
Cn chu y rng:
Hng s cn bng khng co n v. Khi thit lp phng
trnh hng s cn bng ngi ta quy c ap sut ring
phn (nng ) cua cac cht vit v phai cua phng
trnh hoa hoc (cac san phm) t t s, con cac cht
tham gia t mu s.
V cac s mu trong biu thc cua phng trnh hng s
cn bng ng vi cac h s ty lng trong phng trnh
phan ng nn s dung ung gia tr cua hng s cn
bng cn phai bit phan ng c vit di dang nao
trong cac cach co th.
V du: Phan ng gia N
2
(k) va H
2
(k) co th vit theo hai
cach. Mi cach ng vi mt gia tr cua hng s cn bng
K
p
.
N
2
(k) + 3H
2
(k) 2NH
3
(k) th:
4
3
2
10 . 64 . 1
2 2
3

H N
NH
P
P P
P
K
t
0
= 400
0
C
1/2N
2
(k) + 3/2H
2
(k) NH
3
(k) th:
2
2 / 3 2 / 1
'
10 . 28 , 1
2 2
3

H N
NH
P
P P
P
K

t
0
= 400
0
C.
6.2.2. Mt s phng phap xac nh hng s cn
bng
a. Xac nh hng s cn bng theo nng cac cht
thi im cn bng
Nu bit nng ban u cua cac cht tham gia th ch
cn xac nh nng cua mt trong cac cht tham gia
hoc tao thanh luc cn bng la u tnh c nng
cua cac cht con lai luc cn bng bng cach da
vao phng trnh phan ng.
b. Xac nh hng s cn bng da vao cac d kin
nhit ng hoa hoc
T G
0
T
= - RT lnK
P
=>
1
]
1

RT
G
K
T
P
0
exp
(6-7)
Da vao cac d kin nhit ng ta tnh c
0
T
G = H
0
- TS
0
. T o tnh c K
P
.
c. Hng s cn bng cua phan ng co cht rn tham
gia
52
Trong trng hp co cht rn tham gia vao phan ng va
chung khng tao dung dch rn vi nhau va vi cht kh th
chung khng co mt trong phng trnh cua hng s cn
bng.
Xet phan ng: FeO (r) + CO (k) Fe (r) + CO
2
(k)
Khi cn bng c thit lp:
P T
K RT G ln
0
;
CO
CO
P
P
P
K
2
6.3. S CHUYN DCH CN BNG

6.3.1. S chuyn dch cn bng
Phan ng: aA + bB eE + dD khi at ti cn bng
th:
0
.
.
ln ln
,
_

b
B
a
A
d
D
e
E
P T
P P
P P
K RT G
Nu h ang trang thai cn bng ma ta thay i mt
trong cac thng s trang thai cua h (P, C, T) th noi chung
h thc trn se thay i (G
T
0) va h se tin trin
at ti trang thai cn bng mi ng vi cac gia tr mi cua
ap sut ring phn (nng ) cua cac cht tham gia va san
phm.
S chuyn h t mt trang thai cn bng nay sang
mt trang thai cn bng khac di anh hng cua tac
ng bn ngoai ln h c goi la s chuyn dch cn
bng.
6.3.2. Anh hng cua ap sut
Ta co: K
P
= K
N
P
n
; lnK
N
= lnK
P
- nlnP =>
RT
V
P
n
P
K
T
N

,
_
ln
(6 -8)
+ Nu n > 0: ngha la s phn t kh v phai ln hn
s phn t kh v trai cua phng trnh phan ng th khi
ap sut chung cua h (P) tng th K
N
se giam va cn bng cua
phan ng dch chuyn t phai sang trai.
+ Nu n < 0: th khi P tng, K
N
se tng va cn bng dch
chuyn t trai sang phai.
+ Khi n = 0 th
0
ln

,
_
T
N
P
K
va cn bng khng b chuyn
dch.
V ap sut t l vi s phn t kh nn mt h ang
trang thai cn bng, ta tng ap sut chung cua h (bng
cach lam giam th tch h) th cn bng se chuyn dch
theo chiu phan ng lam giam s phn t kh tc la lam
giam ap sut) va ngc lai.
V du: nu phan ng: N
2
(k) + 3H
2
(k) 2NH
3
(k) ang
trang thai cn bng ma ta tng ap sut chung cua h th cn
bng cua phan ng se chuyn dch theo chiu tao thanh
NH
3
(hiu sut cua phan ng tng).
6.3.3. Anh hng cua nhit
53
T:
RT
G
K
T
P
0
ln

( )
2
T
H
T
T
G
T
P

1
1
1
1
]
1
=>
2
0
0
ln
RT
H
T
K
T
P
P

,
_
(6
-9)
Nh vy, nu mt h ang trang thai cn bng, ta tng
nhit cua h th cn bng se dch chuyn theo chiu
cua phan ng thu nhit (lam giam nhit cua h, chng
lai s tng cua ta); con nu ta giam nhit cua h th
cn bng se dch chuyn theo chiu cua phan ng toa nhit
(lam tng nhit cua h, chng lai s giam cua ta)
Trong khoang nhit rt hep co th coi const H
T

0
, khi o
tch phn phng trnh (7-14) ta c:
1
]
1

1 2
0
1
2
1 1
) (
) (
ln
T T R
H
T K
T K
T
P
P
(6 -10)
6.3.4. Anh hng cua nng
Xet phan ng: aA + bB eE + dD
Khi cn bng c thit lp:
const
C C
C C
K
b
B
a
A
d
D
e
E
C

.
.
T = const.
Nu h ang trang thai cn bng ma ta thm mt trong
cac cht tham gia hoc ly i mt trong cac cht san phm
(gi th tch va nhit khng i) th cn bng phai
chuyn dch theo chiu lam giam nng cua cac cht
tham gia va lam tng nng cua cac cht san phm
gi cho t s
const
C C
C C
b
B
a
A
d
D
e
E
.
.
, ngha la theo chiu t trai sang
phai.
6.3.5. Nguyn l chuyn dch cn bng Le Chatelier
Nm 1887, Le Chatelier khai quat hoa anh hng cua cac
yu t ln s chuyn dch cn bng bng mt nguyn l
c goi la nguyn l chuyn dch cn bng hay nguyn l Le
Chatelier: Nu mt h ang trang thai cn bng ma ta
thay i mt trong cac thng s trang thai cua h (ap sut,
nhit , nng ) th cn bng se chuyn dch theo chiu
co tac dung chng lai s thay i o. Nguyn l Le
Chatelier khng nhng ch ung cho cac phan ng hoa hoc
ma con ung cho moi qua trnh bt ky khac.
===================
54
PHN TH T
DUNG DCH VA DUNG DCH
IN LI
CHNG 7
DUNG DCH
7.1. PHN TH NHT: KHAI QUAT V DUNG DCH
7.1.1. H phn tan
Mt h gm hai (hay nhiu cht) trong o mt cht
dang cac hat rt nho c phn b vao trong cht kia th
h o c goi la h phn tan. Cht c phn b goi
la pha phn tan, con cht trong o co pha phn tan phn tan
phn b c goi la mi trng phn tan. Nu cac hat cua
pha phn tan co cung kch thc th h c goi la n
phn tan, trong trng hp ngc lai, cac hat cua pha phn
tan co kch thc to, nho khac nhau th h c goi la a
phn tan.
H phn tan th: la h phn tan trong o kch thc
cua cac hat cua pha phn tan nm trong khoang t 10
- 7
m
n 10
-4
m. H nay khng bn, chung thng b sa lng di
tac dung cua lc trong trng.
Huyn phu va nhu tng la nhng h phn tan th. Huyn
phu la h phn tan trong o pha phn tan la nhng hat cht
rn rt nho con mi trng phn tan la cht long. Nhu
tng la h phn tan trong pha phn tan va mi tng phn
tan u la cht long. V du: nc phu sa la huyn phu, con
sa la nhu tng.
Cac hat cua h phn tan th co th nhn bng knh hin
vi va i khi bng mt thng.
Dung dch keo: la h phn tan trong o cac hat cua
cht phn tan co kch thc trong khoang t 10
- 7
m n 10
- 9
m. Dung dch keo tng i bn. Cac hat keo thng ch
nhn thy di knh siu vi.
Dung dch tht: la h phn tan trong o cac hat cua
pha phn tan bng kch thc cua phn t hoc ion (10
-10
m).
H nay rt bn.
Trong dung dch tht, cac hat cua cht phn tan va cac
phn t cua mi trng co kch thc xp x nhau, khng con
b mt phn chia gia chung, do o toan b dung dch la
mt h ng th. Cht c phn tan goi la cht tan,
con mi trng phn tan c goi la dung mi. Lng cht
tan trong mt lng dung mi xac nh co th bin i trong
55
mt pham vi tng i rng. Dung dch long c tao
thanh khi cho cac cht kh, long, rn hoa tan vao cht long.
Dung dch la mt h ng th long hoc rn gm co
hai hay nhiu cht ma thanh phn cua chung bin i trong
mt pham vi tng i rng.
7.1.2. Nng cua dung dch
Nng la ai lng biu th lng cht tan co trong
mt n v khi lng hoc mt n v th tch dung dch
hay dung mi.
Co nhiu phng phap biu din nng cua dung dch
va co th chia thanh hai nhom: nng co n v va nng
khng co n v.
Nng co n v o
a. Nng phn trm: la s gam cht tan co trong 100 g
dung dch va c xac nh theo cng thc:
100 %
B A
A
C
+
. Trong
o: A, B la lng cht tan va dung mi tnh bng gam.
b. Nng molan: La s mol cht tan co trong 1000 gam
dung mi.
c. Nng mol: (k hiu la C
M
) la s mol cht tan co trong
1 lit dung dch.
d. Nng ng lng gam: (k hiu N) la s ng
lng gam cht tan co trong mt lt dung dch.
Nng khng co n v o
Nng phn mol: c o bng phn mol cua cht
tan va dung mi, no la s mol cua cht tan (dung mi) co trong
mt mol dung dch.
:
i
i
i
i
N
n
n
N
nng phn mol cua i.

7.1.3. S hoa tan, hiu ng nhit cua qua trnh hoa
tan
Hoa tan la qua trnh phn tan cht tan di dang nguyn
t, phn t, ion vao toan b th tch cua dung mi. Khi o
xay ra qua trnh tng tac gia cac phn t cua dung mi vi
cac phn t (ion, nguyn t, phn t) cua cht tan tao
thanh cac hp cht hoa hoc goi la sonvat, (nu dung mi la
nc th goi la hydrat).
Qua trnh phn tan cht tan bao gm s pha v trang thai
tp hp cua cht tan thanh cac ion, nguyn t, phn t va
khuych tan chung vao trong toan b th tch cua dung mi
cn tiu tn mt nng lng H
pt
. S sonvat hoa la qua
trnh hoa hoc toa ra mt nng lng goi la nng lng
sonvat hoa H
s
. (Nu dung mi la nc th goi la nng lng
hidrat hoa H
h
)
Hiu ng nhit cua qua trnh hoa tan (H
ht
) d nhin bng:
H
ht
= H
pt
+ H
s
. V H
pt
> 0 con H
s
< 0 nn nhit hoa tan
H
ht
co th la m hoc dng.
56
Nhit lng thoat ra hay thu vao khi hoa tan cht tan vao
dung mi (nc) goi la nhit hoa tan. Nhit lng thoat ra
hay thu vao khi hoa tan mt mol cht tan vao dung mi (nc)
goi la hiu ng nhit hoa tan.
7.1.4. hoa tan
hoa tan cua mt cht nhit a cho la s gam
cht o tan ti a vao 100 gam dung mi cho dung dch bao
hoa nhit o (k hiu la S). hoa tan cua mt cht
ngoai s phu thuc vao ban cht cua cht tan va ban
cht cua dung mi, con phu thuc vao nhit va ap sut.
Ngi ta quy c: S > 10: d tan.
S < 1: Kho tan.
S < 0,01: coi nh thc t khng tan.
Cho ti nay cha co mt nh lut nao v hoa tan cua
cac cht. Thc nghim cho thy cac cht co cu tao phn
t ging nhau th d hoa tan trong nhau - co ngha la dung
mi phn cc hoa tan tt cac cht tan phn cc va ngc
lai.
a. hoa tan cua cht rn
Qua trnh hoa tan cht tan rn thng co H
pt
> 0 ln con
H
s
< 0 nhng khng m lm nn nhit hoa tan H
ht
thng la
dng (qua trnh thu nhit). V vy, hoa tan cua hu ht
cac cht rn tng khi nhit tng. V du: hoa tan cua
KNO
3
(tnh bng g/100g nc) phu thuc vao nhit nh
sau:Nhit
0
C 0 20 40 60 80 100
hoa tan 13,5 31,5 64 110
169 247
b. hoa tan cua cht long
Cac cht long hoa tan tng h vao nhau co th xay ra
cac trng hp sau:
Hoa tan hoan toan: v du glyxrin hoa tan trong nc theo
bt ky ty l nao.
Hoa tan han ch: v du thm dn tng giot phenol vao
nc va lc. u tin phenol tan nhng n mt luc nao o
se phn hai lp dung dch nm cn bng la phenol bao hoa
nc va nc bao hoa phenol.
Hoan toan khng hoa tan: v du cho benzen vao nc se
phn hai lp: lp trn la benzen con lp di la nc .
c. hoa tan cua kh. nh lut Henry
Qua trnh hoa tan cua kh nh a noi trn thng kem
theo s giai phong nng lng. Do o, khi tng nhit th
cn bng: kh (trn mt cht long) kh (hoa tan) chuyn
dch t phai sang trai ngha la hoa tan cua kh giam i. Khi
tng ap sut th cn bng trn dch chuyn t trai sang phai,
hoa tan cua kh se tng ln. Ta co: m = kp (7-1)
nh lut Henry: nhit khng i, khi lng cht
kh hoa tan trong mt th tch cht long xac nh t l
thun vi ap sut cua kh nm cn bng trn b mt cht
57
long. nh lut Henry ch ung vi cac kh co hoa tan
nho, khng tac dung hoa hoc vi dung mi va ap sut
khng qua ln.
7.2. PHN TH HAI: TNH CHT CUA DUNG DCH
S co mt cua cht tan va tng tac gia cac phn t
cht tan vi cac phn t cua dung mi lam cho tnh cht cua
dung dch khac vi tnh cht cua dung mi nguyn cht. Trong
pham vi chng trnh, ta gii han vic nghin cu tnh
cht cua dung dch loang cha cht hoa tan khng iin li,
khng bay hi va khng tao dung dch rn vi dung mi.
7.2.1. Ap sut hi bao hoa - inh lut Raoult 1.
Tai cung mt nhit , ap sut hi bao hoa cua dung
dch cha cht hoa tan khng in li, khng bay hi lun nho
hn ap sut hi bao hoa cua dung mi nguyn cht.
Nu goi N
1
la nng phn mol cua dung mi P
1
va P
1.0
ln lt la ap sut hi bao hoa cua dung dch va ap sut
hi bao hoa cua dung mi nguyn cht cung mt nhit
th bng thc nghim nm 1887 nha vt l Phap Raoult a
thit lp c: P
1
= N
1
.P
1.0
.
Nhng: N
1
= 1 - N
2
nn: P
1
= (1 - N
2
).P
1.0
Hay:
2 1
2
2
0 . 1
2
0 . 1 0 . 1
1 0 . 1
n n
n
N
P
P
N
P
P
P
P P
+

>
(7-2)
Vi:
0 . 1
P
P
: giam ap sut hi bao hoa tng i cua
dung dch, n
1
, n
2
la s mol dung mi va s mol cht hoa tan.
nh lut Raoult co th phat biu nh sau: giam ap
sut hi bao hoa tng i cua dung dch loang cha cht
hoa tan khng bay hi t l vi s mol cua cht hoa tan co
trong mt lng dung mi xac nh.
Vi dung dch loang n
1
>>n
2
, th n
1
+ n
2
n
1
va
M n
m
n
n
P
P
1 1
2
0 . 1

.
T y ta co th xac nh c M cht tan nu o c ap
sut bao hoa cua dung dch (m la lng cht hoa tan co
trong n
1
mol dung mi va M la khi lng mol cua cht hoa
tan).
7.2.2. Nhit si va nhit ng c cua dung
dch
Nhit si cua 1 cht la nhit tai o, ap sut hi
cua no bng ap sut ngoai. Khi nng cua dung dch cang
ln th nhit si cua dung dch cang tng, con nhit
ng c cua dung dch cang giam. Khac vi dung mi nguyn
cht, trong qua trnh si nhit cua dung dch tip tuc
tng va trong qua trnh ng c nhit cua dung dch tip
tuc giam.
58
V mt nh lng, Raoult a thit lp c rng:
giam nhit ng c va tng nhit si cua dung
dch loang cha cht hoa tan khng in ly, khng bay hi ty
l vi lng cht tan co trong mt lng dung mi xac
nh.
Nu goi m la khi lng cht tan (tnh bng gam) co
trong 1000 gam dung mi va M la khi lng mol cua cht tan
th:
M
m
k t
M
m
k t
d d s s
;
(7-3)
Trong o: T
s
la tng nhit si, t
la giam nhit
ng c cua dung dch so vi dung mi nguyn cht, con
K
s
va K
la nhng h s ty l ch phu thuc vao ban cht

cua dung mi, K
s
c goi la hng s nghim si va K

c goi la hng s nghim ng. Vi dung mi phn cc
manh nh nc th K
s
= 0,52; K
= 1,86, con dung mi khng

phn cc nh benzen th K
s
= 2,64; K
= 5,07.
Ta co th xac nh c khi lng cua phn t cht
tan khng bay hi bng cach o nhit si va nhit ng
c cua dung dch loang cua chung.
7.2.3. Ap sut thm thu
Ta hay lam th nghim sau:Nhung bnh A, thanh cua no la
mt mang ban thm (mang nay ch cho cac phn
t cua dung mi i qua va ngn cac phn t cua
cht hoa tan lai), dung dch ng vao cc
nc B (hnh 5), mt luc sau thy ct dung dch
trong bnh A dng ln dn va ti cao h th dng
lai. Hin tng cac phn t dung mi i qua mang
ban thm c goi la s thm thu. Tnh cht
thm thu cua dung dch c c trng bng
mt ai lng goi la ap sut thm thu. V
gia tr no bng ap sut cn tac dung ln dung
dch lam ngng s thm thu.
Trong th nghim trn, ap sut thm thu chnh
bng ap sut thuy tnh cua ct dung dch co
chiu cao la h. Thc nghim cho thy chiu cao h
khng phu thuc vao hnh dang cua bnh A ma ch
phu thuc vao nhit va nng cua dung
dch.
Da vao s phn tch cac kt qua thc nghim va da
vao nhn xet v s tng tac gia cht hoa tan va cht
kh nm 1886, Vant Hoff phat biu mt nh lut nh sau:
Ap sut thm thu cua dung dch la ap sut co c khi
cht hoa tan trang thai kh, co nhit bng nhit
cua dung dch va chim mt th tch bng th tch cua
dung dch. Biu thc toan hoc cua nh lut nay chnh la
phng trnh trang thai kh l tng Clapeyron - Mendeleep:
RT
M
m
PV
=> PV = nRT = CRT (7-4)
59
h
Hnh 7.1. S
th nghim ap
sut thm thu
Trong o: P la ap sut thm thu cua dung dch cha m
gam cht tan trong th tch dung dch V (lt) va nhit T
(K), M: khi lng mol cua cht hoa tan; R la hng s kh va
C la nng mol/lt.
Ghi chu: Cac nh lut Raoult va Vant Hoff (v ap sut
thm thu) ch ung vi cac dung dch loang cha cht tan
khng bay hi va khng in li.
CHNG 8
DUNG DCH CHT IN LY
8.1. THUYT IN LY
8.1.1. Tnh cht bt thng cua cac dung dch axit,
baz va mui.
Thc nghim cho thy ap sut thm thu, giam ap
sut hi bao hoa tng i, tng nhit si, giam
nhit ng c cua cac dung dch axit, baz va mui o
c t thc nghim lun lun ln hn so vi tnh toan theo
l thuyt. V du: giam nhit ng c cua dung dch
cha 1 gam NaCl trong 100 gam nc tnh theo cng thc cua
Raoult:
0
318 , 0
5 , 58
10
86 , 1
M
m
k t
d d . Nhng gia tr thc t o
c la 0,617
0
, ngha la ln hn gn gp 2 ln so vi tnh
theo l thuyt.
phu hp vi thc nghim, Vant Hoff ngh a vao
cac cng thc tnh ap sut thm thu, giam ap sut hi
bao hoa tng i, tng nhit si va giam nhit
ng c mt h s i, goi la h s Vant Hoff. Ta co:
p
p
t
t
P
P
i

' ' '
. (8 -1).
Nh vy: h s i cho bit ap sut thm thu (P),
giam ap sut hi bao hoa tng i (
0 . 1
'
P
P
), tng nhit
si va giam nhit ng c (t) o c bng thc
nghim ln hn so vi tnh theo l thuyt (P, p/p
1.0
, T) bao
nhiu ln.
Gia tr cua i c xac nh bng thc nghim. i vi
cac dung dch cua cac cht khac nhau, i co cung gia tr khac
nhau va khi dung dch cang loang th i cang tin dn ti 2, 3,
4.
8.1.2. Thuyt in li
a. Thuyt in li cua Arrrhenius: Theo Arrrhenius hin
tng cac phn t phn li thanh ion goi la s in li hay la
s ion hoa. Nhng cht khi hoa tan vao dung mi, cac phn
t cua chung phn li thanh ion goi la cht in li. Qua trnh
phn li lam cho s tiu phn (ng ngha vi no la nng )
co trong dung dch tng ln. Nh th, nguyn nhn cua tnh
cht bt thng va tnh dn in cua cac dung dch axit,
60
baz va mui la s in li cac phn t cua chung thanh cac
ion. Thuyt Arrhenius giai thch c tnh bt thng va tnh
dn in cua cac dung dch axit, baz va mui.
b. Thuyt in li cua Cablucp: Theo Cablucp, nguyn
nhn c ban cua s in li la s tac dung tng h gia
cht in li va cac phn t dung mi tao thanh cac ion b
sonvat hoa.
S in li cua hp cht ion: Xet s in li cua
NaCl trong nc
Cac ion Na
+
va Cl
-
nm trn b mt tinh th do dao ng
khng ngng va do tng tac vi cac phn t H
2
O phn t
tach ra khoi mang li tinh th va i vao dung dch di
dang ion b hirat hoa (hnh 10.1). Nh vy, co th biu
bin s in li cua NaCl bng phng trnh sau:
NaCl + mH
2
O = Na
+
.nH
2
O + Cl
-
(m-n)H
2
O
T s trn ta thy rng cac ion trong dung dch khac
vi cac ion nm trong mang li tinh th. Thc vy, ion
Cu
2+
trong tinh th CuSO
4
khan khng mau nhng trong dung
dch nc co mau xanh da tri v kt hp thm 4 phn t H
2
O
tao thanh Cu
2+
.4H
2
O
S in li cua hp cht phn cc
Cac phn t co lin kt cng hoa tr co cc khi hoa tan
vao nc cung phn li thanh cac ion.
HCl + nH
2
O = H
3
O
+
+ Cl
-
(n-1)H
2
O ; (H
3
O
+
la ion
hirxni).
61
Na
Na
C l
Cl
Cl
Cl
Na Na
Na Na
Cl
Cl
Cl
C l
Cl
Cl
Cl
Cl
Cl
C l
Cl
Cl
Cl
Cl
Na Na
Na Na
Hnh 8.1. S in li
cua NaCl
Na Cl Na Na
Hnh 8.2. S in li cua phn t
phn cc HCl
Nh vy kt qua cua s in li khng phai tao thanh cac
ion t do ma tao thanh nhng ion b hirat hoa.
8.1.3. Cn bng trong dung dch cua cht in li yu
a. Cht in li manh va cht in li yu
Cht in li manh la cht khi hoa tan vao nc th tt ca
cac phn t cua chung phn li thanh ion, ngha la trong dung
dch khng con cac phn t khng in li. Cac axit manh, baz
manh va a s cac mui tan la cht in li manh. Dung
dch cua chung dn in tt. ch s in li hoan toan,
trong phng trnh in li ghi du (=); V du: NaCl = Na
+
+ Cl
-
Cht in li yu la cht khi hoa tan vao nc ch mt
phn cac phn t phn li thanh ion. Trong dung dch cua cac
cht in li yu, cac phn t khng phn li nm cn bng
ng vi cac ion cua chung. Dung dch cua chung dn in
kem. biu th cn bng ng nay ta dung du . V
du: CH
3
COOH H
+
+ CH
3
COO
-
b. in li : c trng cho manh, yu cua
cht in li ta dung in li . o la ty s phn t phn li
trn s phn t hoa tan: = s phn t phn ly/ s phn t
hoa tan. (0 < 1). V du: dung dch HCH
3
COO 0,1M co
in li la:1,32% th trong mt lt co 0,00132 mol phn li,
c. Hng s in li: Xet s in li cua cht in li yu
AB: AB A
+
+ B
-
,
Vi la in li cua AB. Ta co:
] [
] ][ [
AB
B A
K
+

(8 -2)
Hng s cn bng K y goi la hng s in li, no
c c trng cho kha nng in li cua mt cht. Gia tr
K cang ln th s in li cang manh va ngc lai. i
vi mt cht in li cho trc, hng s in li K ch phu
thuc vao nhit .
d. S lin h gia hng s in li va in li.
nh lut pha loang Ostwald
Goi C la nng mol.l
-1
cua cht in li AB va la
in li cua Ab.
Ta co: AB A
+
+ B
-
;
C 0 0
C C C
C C C C
=>

1
.
2
C
C C
C C
K (8
-3).
y la biu thc cua nh lut pha loang OstWald. T (10-3)
thy rng khi tng th 1- giam, do o
2
/(1 - ) se tng.
nhit khng i K la mt hng s do o mun cho
const C

1
2
th C phai giam, ngha la loang cua dung dch
62
phai tng. Dung dch cang loang th in li cang ln va
ngc lai. Khi loang (1/C) tin ti v cung th 1.
Biu thc (8-3) cho phep tnh in li cac nng
khac nhau nu bit hng s in li. Ngc lai, nu bit
in li mt nng nao o th tnh c hng s
in li.

e.
Cac
phng phap xac nh in li
Xac nh in li theo h s h s Vant Hoff
i: Nu goi N la s phn t hoa tan, la in li va q la
s ion ma mt phn t phn li ra th:
+ S phn t ph li se la: N.
+ S phn t khng phn li: N - N.
+ S ion co trong dung dch: qN.
=> S phn t co trong dung dch: N = s ion + s phn
t khng phn li
=> N = qN = N -N = N (q + 1 - ). Nhng:
( )
N
q N
N
N
i
+

1 '

T o:
1
1

q
i
Bit i co th tnh c va ngc
lai. (8 -4) .
Xac nh in li bng cach o dn in:
Trong thc t, thng xac nh in li cua mt cht
nng nao o bng cach o dn in cua dung dch.
xac nh in li ngi ta khng o dn in ring
ma o dn in ng lng cua dung dch. dn
in ng lng la dn in cua mt th tch dung
dch cha mt ng lng gam cua cht in li. No ch
phu thuc vao in li. Cht nao in li cang manh th
dn in ng lng cang ln va ngc lai.
Nu goi C la nng ng lng gam th V = 1000/C
(ml) chnh la th tch cha mt ng lng gam cua cht
in li. Nu goi la dn in cua 1 cm
3
dung dch nay
63
1
V = 1/C
Hnh 8.3. S phu thuc cua in li vao loang
(1/C) cua dung dch.
th dn in ng lng cua dung dch se la:
C
V
1000
. .
; o c se tnh c .
dn in ng lng loang v cung goi tt la
dn in v cung va k hiu la

=>

(*). dn
in ng lng v cung
cua mt cht co mt gia tr

xac nh nn t (*) thy rng nu o c dn in
ng lng th co th xac nh c in li bt
ky nng nao.
f. S chuyn dch cn bng ion: S chuyn dch cn
bng trong dung dch axit axtic:
CH
3
COOH H
+
+ CH
3
COO
-
Nu a vao dung dch cht CH
3
COONa (ngha la ion cua
cht in li yu phn li ra) th cn bng se chuyn dch v
pha trai va in li se giam.
8.2. THUYT AXITS - BAZ
8.2.1. c tnh chung cua cac axt va baz
c tnh chung cua cac axit: co v chua, phan ng vi baz
tao thanh mui, phan ng vi mt s kim loai cho hiro
thoat ra, lam bin i mau cua cac cht ch th (v du bin
quy tm thanh o).
c tnh chung cua cac baz: co v xa phong, phan ng
vi axit tao thanh mui. Lam bin i mau sc cua cac
cht ch th (v du lam xanh quy tm);
8.2.2. Cac thuyt axits - baz
a. Thuyt axit va baz theo Arrhenius:Theo Arrhenius th:
Axit la nhng hp cht cha hiro khi hoa tan voa nc
cac phn t cua chung phn li thanh ion H
+
.
Baz la moi hp cht cha nhom hiroxyl OH va khi hoa tan
vao nc cac phn t cua chung phn li thanh ion OH
-
Thuyt axit - baz cua Arrhenius a giai thch c nhiu
d kin thc nghim. Thiu sot c ban cua Arrhenius la a
khng y ti vai tro cua dung mi va a gn tnh baz vi
ion OH
-
.
b. Thuyt axit va baz theo Bronsted (J.Bronsted - an
Mach)
+ Axit la nhng cht (phn t, nguyn t, ion) co kha nng
nhng proton H
3
O
+
. Bao gm: H
+
, NH
4
+
, Al
3+
, Fe
3+
, Fe
2+
, Cu
2+
,
Zn
2+
, HSO
4
-
...
+ Baz la nhng cht (phn t, nguyn t, ion) co kha nng
kt hp proton H
3
O
+
. Bao gm: OH
-
, CO
3
2-
, PO
4
3-
, NO
2
-
, S
2-
, SO
3
2-
,
AlO
2
-
, ZnO
2
2-
, CH
3
-COO
-
, C
6
H
5
O
-
, ....
+ Lng tnh la nhng cht va co kha nng cho, va co
kha nng kt hp proton H
3
O
+
. Bao gm: Al(OH)
3
, Zn(OH)
2
,
Be(OH)
2
, Al
2
O
3
, Cr
2
O
3
, ZnO, BeO, CH
3
COONH
4
, (NH
4
)
2
CO
3
, HCO
3
-
, ....
64
+ Trung tnh la nhng cht khng co kha nng cho, khng co
kha nng kt hp proton H
3
O
+
. Bao gm: Na
+
, K
+
, Ca
2+
, Ba
2+
, ...;
Cl
-
, NO
3
-
, SO
4
2-
....
lam sang to thuyt axit - baz cua bronsted ta hay nhn
xet phan ng in li ca HCl trong dung mi la nc:
HCl + H
2
O H
3
O
+
+ Cl
-
Axit 1 baz 2 axit 2 baz 1
Trong phan ng trn, HCl nhng prton cho H
2
O. Vy, HCl la
mt axit va H
2
O la mt baz. Trong phan ng nghch, H
3
O
+
nhng prton cho Cl
-
. Vy, H
3
O
+
la mt axit, con Cl
-
la mt
baz. HCl c goi la axit lin hp cua Cl
-
, H
2
O la baz lin
hp cua H
3
O
+
. V vy: HCl - Cl
-
va H
3
O
+
- H
2
O la cp axit - baz
lin hp.
manh cua mt cp axit - baz nao o ngoai s phu
thuc vao ban cht cua cp axit - baz cung tn tai vi no.
iu o cung co ngha la khai nim axit - baz co tnh tng
i. Tht vy, trong phan ng (a) H
2
O la mt baz, nhng
trong phan ng:
NH
3
+ H
2
O NH
4
+
+ OH
-
th H
2
O ong vai tro la mt
axit.
T s trnh bay trn, ta thy mun so sanh manh
cua cac cp axit - baz khac nhau phai o tnh axit cua chung
i vi cung mt cp axit - baz ly lam chun. Co th
dung nhiu cp chun nhng y ta xet dung dch nc
nn cp H
3
O
+
- H
2
O c ly lam chun. Thang nay goi la
thang axit - baz i vi nc.
c. Thuyt axit va baz theo Lowry (T.Lowry - Anh)
+ Axit la nhng phn t, nguyn t, ion . V du: H
+
, Al
3+
....
+ Baz la nhng phn t, nguyn t, ion co mt hoc
nhiu cp electron cha s dung. V du: OH
-
, NH
3
....
Trong pham vi chng trnh, ta khao sat chi tit thuyt
prton cua Bronsted va dung no tnh pH cua cac dung dch
nc cua axit, baz va mui.
8.2.3. Tch s ion cua nc - Ch s hiro ( pH)
Tch s ion cua nc: Nc nguyn cht, tuy vi mc
rt nho cung in li theo phng trnh: 2H
2
O H
3
O
+
+
OH
-
. Trong nc nguyn cht: [H
3
O
+
] = [OH
-
] = O H
K
2
.
25
0
C: [H
3
O
+
] =
14
10
= 10
-7
mol.l
-1
.
+ Mi trng trung tnh: [H
3
O
+
] = [OH
-
] va 25
0
[[H
3
O
+
] = 10
-7
mol.l
-1
.
+ Mi trng axit la mi trng trong o [H
3
O
+
] > [OH
-
] va
25
0
C [H
3
O]
+
> 10
-7
mol.l
-1
.
+ Mi trng kim la mi trng trong o [H
3
O
+
] < [OH
-
] va
25
0
C [H
3
O
+
] < 10
-7
mol.l
-1
.
Ch s hiro ( axit pH)
Biu th axit hoc kim cua c bng nng
ion H
3
O
+
rt khng co li v co luy tha m va thng la s
65
thp phn. Nm 1920, Sorensen a ra khai nim ch s hiro
hay pH: Trong dung dch, nu [H
3
O
+
] = 10
-a
th pH = a, ngha
la: pH = - lg[H
3
O
+
]. (8 -5).
Bang 8.1. S lin quan gia gia tr cua pH va tnh cht
cua mi trng:
[H
3
O
+
] 1 10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-8
10
-9
10
-10
10
-11
10
-12
10
-
13
10
-14
axit tng Trung
tnh
kim tng
PH 0 1 2 3 4
5 6
7 8 9 10 11 12 13
14
Hng s axit, hng s in li
Xet s tng tac cua axit HA vi dung mi B: HA + B BH
+
+ A
-
Hng s in li trong dung mi B:
B HA
BH
HAB
a a
a a
K
.
.
+
Nu dung mi B la nc: HA + H
2
O H
3
O
+
+ A
-
th
O H HA
O H
a a
a a
K
2
3
.
.
'
+

V hoat cua H
2
O co th coi nh khng i nn:
HA
O H
a O H
a
a a
K a K
+

.
'.
3
2
(8 -6).
K
a
la hng s in li cua axit HA trong nc.
Theo tnh cht chung cua hng s cn bng, hng s in li
cua axit HA trong nc ch phu thuc vao nhit , nhit
khng i no la mt hng s va c trng cho kha nng
in li cua HA trong nc: K
a
cang ln th axit HA cang manh.
Ngi ta quy c:
K
a
10
-1
: axit manh.
10
-5
< K
a
< 10
-1
:axit manh trung bnh.
K
a
< 10
-5
:axit yu.
Tnh pH cua cac dung dch axit, baz va mui
a) Tnh pH cua dung dch axit manh: Xet dung dch axit
manh HA co nng C
a
.
HA + H
2
O = H
3
O
+
+ A
-
va 2H
2
O H
3
O
+
+ OH
-
Tn tai ng thi 4 phn t: H
3
O
+
, A
-
, OH
-
, H
2
O.
Vi HA in li hoan toan nn:
[ ] [ ]
[ ]
+
+
+
O H
K
C O H A C
O H
a a
3
3
2

Hay: [ ] [ ] 0
2
3
2
3

+ +
O H a
K O H C O H . Giai ra:
[ ]
2
4
2
2
3
O H a a
K C C
O H
+ t
+
(8-7)
Ta ch co th ly nghim [H
3
O
+
] > 0 (ng vi du +). Nu
dung dch HA khng qua loang th [OH
-
] << [H
3
O
+
]. Ta co th bo
qua nng [OH
-
] trc [H
3
O
+
] cua dung dch nn:
66
[H
3
O
+
] [A
-
] = C
a
=> pH = - lg[H
3
O
+
] = - lgC
a
(8-8)
b) Tnh pH cua dung dch baz manh: Xet dung dch baz
manh B nng C
b
2H
2
O H
3
O
+
+ OH
-
va B + H
3
O
+
= BH
+
+ H
2
O
V B la mt baz manh nn phan ng sau xay ra hoan toan.
Ta co:
[ ] [ ]
+
OH O H K
O H
.
3
2
;
[ ]
[ ]
b
O H
C O H
O H
K
+
+
+
3
3
2
[OH
-
] = [H
3
O
+
] + [BH
+
] [ ] [ ] 0
2
3
2
3
+
+ +
O H b
K O H C O H
Giai phng trnh bc 2 i vi [H
3
O
+
] ta c hai nghim:
[ ]
2
4
2
2
3
O H b b
H C C
O H
+ t
+
(8-9)
Ch ly c nghim [H
3
O
+
] > 0 (nghim ng vi du +)
Nu dung dch baz khng qua loang th [H
3
O
+
] << [OH
-
] va ta
co th bo qua [H
3
O
+
] trc [OH
-
] [OH
-
] [BH
+
] = C
b
;
[ ]
[ ]
b
O H
C OH
K
O H
14
3
10
2

+

=> pH = -lg[H
3
O
+
] = 14 + lgC
b
(8-10) c) Tnh
pH cua dung dch axit yu: Trong dung dch tn tai ng
thi hai cn bng:
HA + H
2
O H
3
O
+
+ A
-
va 2H
2
O H
3
O
+
+
OH
-
Trong dung dch co cac phn t: HA, H
3
O
+
, OH
-
, A
-
va H
2
O
S gn ung cp 1: Nu dung dch axit la u manh th
[OH
-
] << [H
3
O
+
] va ta co th bo qua [OH
-
] trc [H
3
O
+
]; T
[H
3
O
+
] [A
-
] ; [HA] = C
a
- [A
-
] = C
b
- [H
3
O
+
].
Khi o ta co: [H
3
O
+
]
2
+ K
a
[H
3
O
+
] - K
a
C
a
= 0
[ ]
[ ]
+
+
O H C
O H
K
a
a
3
2
3
Hay :
[ ]
2
4
2
3
a a a a
C K K K
O H
+ t
+

(8 -11)
S gn ung cp 2:Nu axit rt yu va nng axit
khng qua nho th [A
-
] << [HA]
Ta co: [H
3
O
+
] [A
-
] va HA] = C
a
=>
[ ]
a
a
C
O H
K
2
3
+
=> T o:
[ ]
a a
C K O H .
3

+
(8 -12)
d) Tnh pH cua dung dch baz yu: Trong dung dch baz
yu th:
2H
2
O H
3
O
+
+ OH
-
va B + H
3
O
+
BH
+
+ H
2
O
Trong dung dch co cac phn t: HA, H
3
O
+
, OH
-
, A
-
va H
2
O
S gn ung cp 1: Nu dung dch u kim th [H
3
O
+
]
<< [OH
-
] va ta co th bo qua [H
3
O
+
] trc [OH
-
] => Phng
trnh bc 2 i vi [H
3
O
+
]: C
b
[H
3
O
+
]
2
- O H
K
2
[H
3
O
+
] - K
a O H
K
2
= 0
67
T o: [ ]
b
O H a b O H O H
C
K K C K K
O H
2
4
2 2 2
2
3
+ t
+
(8-13)
S gn ung cp 2: Nu baz rt yu (K
a
rt ln) va
nng baz khng qua nho th [BH
+
] << [B]. Ta co th bo
qua [H
3
O
+
] trc [OH
-
] va [BH
+
] trc [B].
O H
b
O H
b
a
K
O H C
O H K
O H C
K
2 2
2
3
3
3
] [
] /[
] [
+
+
+

T o:
b O H a
C K K O H / ] [
2
3

+
(8-14)
8.2.4. Cht ch th mau
Cht ch th mau la cht co mau mau sc bin i theo
nng cua ion H
3
O
+
.
Cht ch th mau thng la cac axit hoc baz hu c yu
ma mau cua ion khac mau cua phn t khng phn li. V du,
quy la mt axit hu c yu, phn t cua no co mau o
nhng ion cua no co mau xanh.
Mau cua cht ch th trong dung dch d nhin do t s nng
cua HCtm va Ctm
-
quyt nh. Nhng ty s nay lai do
pH cua dung dch xac nh. Tht vy:
HCtm + H
2
O H
3
O
+
+ Ctm
-
] [
] ][ [
3
HCtm
Ctm O H
K
a
+
T o:
[ ]
[ ]
1
]
1
+
Ctm
HCtm
K O H
a 3
hay
[ ]
[ ] HCtm
Ctm
pK pH
a
+ lg
(8-15)
Vy, mau cua cht ch th khng bin i lin tuc theo
pH cua dung dch ma ch bin i trong khoang t pK
a
- 1
n pK
a
+ 1. Khoang pH trong o mau cua cht ch th bin
i c goi la khoang chuyn mau.
Bang sau cho bit khoang chuyn mau (min gach cheo)
cua quy, metyl da cam va phenolphtalin va mau cua chung
trong cac dung dch co pH khac nhau.
PH 0 3,1 4,4 7 8 10
11 14
Mtyl da
cam
Hng Da
cam
Vang
Quy o T
m
xanh
Phnolphtal
in
Khng mau H
ng
o
thm
T o thy rng, tuy trng hp ma ta dung cac cht
ch th mau khac nhau. V du, mun th mi trng axit phai
dung mtyl da cam ch khng c dung phnolphtalin.
68
8.3. TCH S HOA TAN, IU KIN KT TUA VA HOA TAN
KT TUA CUA CHT IN LI T TAN TRONG DUNG DCH.
8.3.1. Tch s hoa tan: Trong dung dch bao hoa cua cht
in li t tan, tch s nng cac ion la mt hng s.
Hng s o c goi la tch s hoa tan va c k hiu
la T.
8.3.2. iu kin kt tua cua mt cht in li t tan:
Mt cht ch co th kt tua t dung dch khi nng cua
no ln hn hoa tan. T o suy ra: mt cht in li t tan
ch co th kt tua khi tch s nng ion cua no ln hn
tch s hoa tan.
8.3.3. iu kin hoa tan kt tua: Mun hoa tan mt
cht in li t tan th phai thm vao dung dch mt cht nao
o co kha nng kt hp vi mt trong cac ion cua cht in
li t tan tao thanh mt cht in li yu sao cho tch s
nng cac ion cua cht in li t tan lun lun nho hn tch
s hoa tan.
69
PHN TH NM
IN HOA HOC
CHNG 9
CAC QUA TRNH IN HOA
Nng lng cua cac phan ng hoa hoc co th bin thanh
cac dang nng lng khac nh in nng, quang nng va
nhit nng. Ngc lai, co th bin cac dang nng lng
nay thanh hoa nng. Trong chng nay ta se nghin cu s
bin i hoa nng thanh in nng va ngc lai - o la cac
qua trnh in hoa.
9.1. NGUYN TC CHUYN HOA NNG THANH IN NNG
Trong phan ng oxi hoa kh thng thng, electron chuyn
trc tip t cht kh sang cht oxi hoa va nng lng
cua phan ng hoa hoc c bin thanh nhit nng. V du:
Cu
2+
+ Zn = Cu + Zn
2+
Bng cach nao o, nu ta thc hin s oxi hoa Zn
mt ni va s kh ion Cu
2+
mt ni va cho electron chuyn
t cc Zn sang ion Cu
2+
qua mt dy dn th nng lng cua
phan ng hoa hoc se bin thanh in nng. o la cac qua
trnh xay ra trong cac pin.
Hnh 9.1 cho thy s pin Daniel - Iacobi. No gm mt
cc la thanh kem nhung vao dung dch ZnSO
4
va mt thanh
ng nhung vao dung dch CuSO
4
. Hai dung dch nay c ni
vi nhau bng mt ng cha dung dch KCl bao hoa. Khi ni
in cc kem vi in cc ng bng mt dy dn se
thy dong in chay t cc ng sang cc kem trong
mt thi gian dai.
Trong qua trnh hoat ng cua pin, in cc kem b mon
dn, con in cc ng c dy thm ngha la: trn
in cc kem xay ra s oxi hoa kem. Zn - 2e Zn
2+
70
Cu Zn
Hnh 9.1. S pin Daniel -
Iacobi
trn in cc ng xay ra s kh ion Cu
2+
: Cu
2+
+ 2e Cu
Nng lng cua phan ng: Cu
2+
+ Zn Zn
2+
+ Cu a bin
thanh in nng.
Vy, mun bin hoa nng thanh in nng ta phai thc
hin s oxi hoa mt ni va s kh mt ni va cho
electron chuyn t cht kh sang cht oxi hoa qua mt dy
dn. o la nguyn tc hoat ng cua moi pin.
9.2. BC NHAY TH TRN GIANH GII B MT IN CC
VA DUNG DCH
9.2.1. in cc kim loai nhung trong dung dch cha
ion cua no
Khi nhung mt thanh kim loai vao nc nguyn cht th
di tac dung li keo cua cac phn t nc phn cc, cac
ion kim loai tach ra khoi b mt kim loai va i vao dung dch
di dang ion b hirat hoa (hnh 9.2).
Cac electron khng hoa tan trong nc nn lai trn thanh
kim loai, do o thanh kim loai se tch in m va dung dch se
tch in dng. S d in tch m trn b mt kim
loai lam cho ion dng kim loai khng khuych tan c xa
b mt kim loai va tch tu gn o.
Hnh 9.2. Ion kim loai tach ra khoi b mt kim loai va i vao
dung dch
Cn bng: Kim loai + nc ion b hirat hoa +
electron
(trong dung dch) (trn kim
loai)
M + H
2
O M
n+
.mH
2
O + ne c thit
lp rt nhanh.
Kt qua trn ranh gii phn chia kim loai - dung dch co mt
lp in tch kep (hnh 9.3) do o
sinh ra mt bc nhay th.
Tng quat khi nhung kim loai M
vao dung dch L co kha nng sonvat
hoa ion M
n+
th sau mt thi gian
rt ngn, cn bng:
M+ mL =M
n+
.mL + ne (1) se c
thit lp
V tr cn bng cua phan ng
nay phu thuc vao ban cht cua
71
+
+
+
+
+
+
+
+
+
+
+ +
Hnh 9.3. Lp in tch kep
trn ranh
gii phn chia kim loai va dung
dch
Na
Ion b
hyrat
kim loai (c bit la trang thai b mt cua no), ban cht
cua dung mi, nng cua ion M
n+
va nhit . Tnh hoat
ng cua kim loai trong dung dch cang ln th kim loai se
tch in m cang nhiu va hiu s in th gia kim loai
va dung dch cang ln.
9.2.2. in cc tr va dung dch cha cp oxi hoa -
kh
a. in cc tr: la in cc khng chuyn ion cua no vao
dung dch. o la nhng in cc lam bng cac kim loai rt
bn v phng din hoa hoc nh platin, vang...
b. in cc oxi hoa kh: la in cc trong o kim loai
va kh khng tham gia trc tip vao phan ng in cc.
Xet hin tng khi nhung mt in cc tr vao dung dch
cha mt cp oxi hoa - kh noa o. Nu dang oxi hoa
hoat ng manh hn dang kh th dang oxi hoa se n
in cc ly electron va bin thanh dang kh: Oxi hoa +
ne kh.
Noi chung, khi nhung mt in cc tr vao mt dung dch
cha mt cp oxi hoa - kh nao o, cn bng: Oxi hoa +
ne kh se c thit lp.
V tr cua cn bng phu thuc vao ban cht cua cp oxi
hoa - kh, cua dung mi, t s nng cua dang oxi hoa va
dang kh va vao nhit . V du, thanh platin nhung vao
dung dch cua cp oxi hoa kh Fe
3+
/Fe
2+
la in cc oxi hoa -
kh va luc nay ch xay ra: Fe
3+
+ e Fe
2+
. San phm cua
s kh (Fe
2+
) va san phm cua s oxi hoa (Fe
3+
) khng
thoat ra trn in cc ma vn trong dung dch.
Ngoai hai loai in cc kim loai va in cc oxi hoa -
kh trn ta con gp in cc kh - la in cc tip xuc
ng thi vi kh va dung dch cha ion cua no.
9.3. SUT IN NG CUA PIN
9.3.1. H in hoa va k hiu quc t
Mt h gm hai in cc c nhung vao dung dch
in li c goi la h in hoa.
+ Nu h sinh ra dong in th c goi la pin hay
nguyn t Ganvanic.
+ Nu h c ni vi mt ngun in bn ngoai va
cho phep thc hin mt phan ng hoa hoc th c goi
la h in phn.
Theo cng c quc t cua Hip hi quc t hoa hoc l
thuyt va ng dung (International Union of Pure and Applied
Chemistry vit tc la IUPAC) hop nm 1968 tai Stockholm,
mt h in hoa bt k nao cung c k hiu nh sau:
Vt liu in cc 1 - dung dch in cc 1 nhung vao -
dung dch in cc 2 nhung vao - in cc 2. B mt phn
chia hai pha c k hiu bng mt gach thng ng |.
Nu gia hai dung dch khng co th khuych tan th
72
c k hiu bng hai gach thng ng ||, ngc lai
nu co th khuych tan th dung k hiu Nu in cc
hoc dung dch gm nhiu cht th gia cac cht co du
phy.
9.3.2. Sut in ng cua pin - Cng thc Nernst
Mt trong nhng c im cua h in hoa la s oxi
hoa va s kh xay ra hai ni ring bit. Do o, phan ng
tao dong tng cng co th phn thanh hai na phan ng,
mi na phan ng thc hin trn mt in cc nn co
th xem S.. cua pin: E
pin
=
phai

(+)
-
trai

(-)
. Trong o
(+)
va
(-)
la
th cua in cc dng (bn phai) va cc m (bn trai),
chung chnh la hiu s in th gia dung dch va in
cc luc cn bng va c goi la th in cc cn
bng:
'
'
ln
0
i
i
i
n
A
n
A
i i
a
a
nF
RT
+
(9-
1)
Xet pin Daniel - Iacobi Zn|ZnSO
4
||CuSO
4
|Cu
Phan ng xay ra khi pin lam vic: Zn - 2e = Zn
2+
(trn in cc kem)
Cu
2+
+ 2e = Cu (trn in cc
ng)
Gia s pin lam vic mt cach thun nghch (theo ngha
nhit ng hoc) ap sut va nhit khng i:
Ta co:
+
+

2
2
ln
2
0
Cu
Zn
T T
a
a
F
RT
(9-1) =>
+
+
+
2
2
ln
2
0
Zn
Cu
T T
a
a
F
RT
(9-2)
0
T
c goi la sut in ng chun cua pin nhit
T. No phu thuc vao ban cht cua cac cht tham gia
phan ng in cc. Tng quat, nu trong pin xay ra phan
ng:
... ....
'
2
'
2
'
1
'
1 2 2 1 1
+ + + +

t
A n A n A n A n
ne
(*) Th: '
2
'
2
'
1
'
1
2
2
1
1
.
.
ln
2
0
n
A
n
A
n
A
n
A
T T
a a
a a
F
RT
+
(9-3)
y la cng thc Nernst, no biu th anh hng cua nng
cac cht tham gia phan ng in cc ln S.. cua pin.
Phan ng (*) c goi la phan ng tao dong cua pin.
Chuyn s hang th hai cua (9-2) sang logarit thp phn,
thay R = 8,3144 J.K
-1
.mol
-1
va F = 96.484,56 C.mol
-1
vao th cng
thc Nernst 298
0
K co dang:
'
2
'
2
'
1
'
1
2
2
1
1
.
.
ln
059 , 0
0
n
A
n
A
n
A
n
A
T T
a a
a a
n
+
. (9
-3)
73
9.3.3. S phu thuc cua sut in ng cua pin vao
nhit
Ta co: H = -nF
'
,
_

P
T
T
T
(9 -4)
o sut in ng cua pin cac nhit khac nhau co
th tnh c bin thin entropi va entanpi cua cac phan
ng oxi hoa kh. V phep o S.. cua pin cho kt qua vi
chnh xac rt cao (ti milivn) nn y la phng phap xac
nh cac ai lng nhit ng co chnh xac cao.
V du 1: Cho cac cht va cac dung dch sau: Ag , Ag
+
(10
-1
M) ;
Cu, Cu
2+
(10
- 2
M)
Hay ghep chung tao thanh mt pin, ve s va vit
ky hiu cua pin, cho bit chiu cua dong in. Tnh sc
in ng cua pin trn, cho bit:
0
(Ag+/Ag)
= 0,8V;
0
(Cu2+/Cu)
=
0,34V.
Hng dn: K hiu cua pin: Cu|Cu
2+
||Ag
+
|Ag
Cu
2+
/Cu =
0
+ (0,059/2)lg(10)
-2
= 0,34 - 0,059;
Ag
+
/Ag =
0
+ (0,059/1)lg(10)
-1
= 0,8 - 0,059; => E =
0,46V
V du 2: 20
0
C va 30
0
C S.. chun cua pin: Pt, H
2
|HCl.aq||Hg
2
Cl
2
(r), Hg ln lt bng 0,2699 V va 0,2699 V.
Tnh G
0
, H
0
va S
0
cua phan ng:
1/2 Hg
2
Cl
2 (r)
+ 1/2 H
2 (k)
Hg (l) + HCl.aq ( 25
0
C).
Giai: Ta co: G
0
T
= -FE
0
T
Do o: G
0
293
= -96485 C.mol
-1
x 0,2699V
= -26,04 kJ.mol
-1
G
0
303
= -96485 C.mol
-1
x 0,2699V =
-25,775 kJ.mol
-1
( ) ( ) [ ]
( )
1 1
1
0 1 1 0
298
. . 29
15 , 293 15 , 303
. 04 , 26 75 , 25
. 90 , 25 .
2
75 , 25 04 , 26

>

,
_

>

mol K J S
K
mol kJ
S
T
G
mol kJ mol kJ G
P
T o:
( )
1 1 0
298
1 1 1 0
298
0
298
0
298
. 564 , 34 . 35 , 34546
. . 29 15 , 298 . 25900 15 , 298

>
+ +
mol kJ mol J H
mol K J Kx mol J S G H
9.4. TH IN CC
74
Cu
2+
Ag
+
Ag
Cu
e
i
9.4.1. Quy c quc t v phan ng in cc va
th in cc
Cng thc Nernst biu th s phu thuc cua th in
cc cn bng vao nng cac cht tham gia phan ng
in cc nhit T va 25
0
C la:
[ ]
[ ]
'
'
0
ln
i
i
n
i
n
i
i i
A
A
nF
RT
+
;
25
0
C th
[ ]
[ ]
'
'
0
ln
059 , 0
i
i
n
i
n
i
i i
A
A
n
+
(9-5)
Th in cc la S.. cua pin gm in cc hiro tiu
chun ghi bn trai va in cc khao sat ghi bn phai: E =
phai
-
H
+
/Htrai
=
H
(Vi
H
la th in cc so vi hiro).
Mun o th in cc cn bng cua mt in cc nao
o, v du in cc kem, ta phai thit lp mt pin gm
in cc hiro tiu chun (ghi bn trai) va in cc kem
(ghi bn phai), Sau o o S cua pin nay: Pt, H
2
|H
3
O
+
|| Zn
2+
|Zn.
Sut in ng cua pin c coi la dng nu dong in
trong pin i t trai sang phai (dong electron ngc lai i t
phai sang trai), ngc lai se m.
9.4.2. Th in cc tiu chun cn bng
Th in cc tiu chun cua kim loai la S cua pin tao
bi in cc hiro tiu chun ghi bn trai va in cc kim
loai nhung vao dung dch mui cua no hoat ion kim loai
bng 1 ghi bn phai.
Th in cc tiu chun cua mt cp oxi hoa kh (in
th kh tiu chun) la S cua pin tao bi in cc hiro
tiu chun ghi bn trai va in cc platin nhung vao dung
dch cha mt cp oxi hoa kh (ma hoat mi dang
bng 1) ghi bn phai.
Du cua th in cc tiu chun cho bit dang kh
hoat ng manh hn (du m) hay yu hn (du dng)
hiro H
2
con ln cua no cho bit hoat ng manh hn hay
kem hn nhiu hay t.
Th in cc tiu chun cua in cc nao cang nho (tr
s ai s) th dang kh cua no hoat ng cang manh,
con dang oxi hoa cua no hoat ng cang kem va ngc
lai.
V du 1: th in cc tiu chun cua natri rt nho (-
2,714 V) nn kim loai natri (dang kh) hoat ng rt manh:
Na - e = Na
+
rt d. Nhng Na
+
(dang oxi hoa) + e = Na rt
kho.
V du 2: Cp MnO
4
-
, Mn
2+
co th kha tiu chun rt ln
(+1,51 V) nn ion MnO
4
-
co tnh oxi hoa rt manh. Ngc lai
ion Mn
2+
co tnh kh rt manh.
Qua bang gia tr cua th in cc tiu chun trn (sp
xp theo th t
0
tng dn) co th rut ra mt s nhn
xet quan trong sau:
75
+ Cp oxi hoa kh nao co th in cc tiu chun ln
th dang oxi hoa cua no co th oxi hoa c dang kh cua
cp co th in cc tiu chun nho hn.
V du:
V
Zn Zn
763 , 0
0
/
2

+ va
V
Ag Ag
799 , 0
0
/
+
+
nn ion Ag
+
(dang oxi
hoa cua cp Ag
+
/Ag) co th oxi hoa c kem kim loai
(dang kh cua cp Zn
2+
/Zn): Zn + 2Ag
+
= Zn
2+
+ 2Ag
Cp MnO
4
-
, Mn
2+
co th in cc tiu chun ln hn cp
Fe
3+
/Fe
2+
nn ion MnO
4
-
(dang oxi hoa) co th oxi hoa c ion
Fe
2+
(dang kh): MnO
4
-
+ 5Fe
2+
+ 8H
+
= Mn
2+
+ 5Fe
3+
+ 4H
2
O
Bang 9.1. Th in cc tiu chun cua mt s cp oxi
hoa kh
K hiu in cc Phan ng in cc
0
(vn)
Li
+
/ Li
Li
+
+ e Li
-3,045
K
+
/ K
K
+
+ e K
-2,925
Rb
+
/ Rb
Rb
+
+ e Rb
-2,925
Cs
+
/ Cs
Cs
+
+ e Cs
-2,923
Ca
2+
/ Ca
Ca
2+
+ 2e Ca
-2,870
Na
+
/ Na
Na
+
+ e Na
-2,714
Mg
2+
/ Mg
Mg
2+
+ 2e Mg
-2,370
Be
2+
/ Be
Be
2+
+ 2e Be
-1,850
Al
3+
/ Al
Al
3+
+ 3e Al
-1,660
Mn
2+
/ Mn
Mn
2+
+ 2e Mn
-1,180
Zn
2+
/ Zn
Zn
2+
+ 2e Zn
-0,763
Cr
3+
/ Cr
Cr
3+
+ 3e Cr
-0,740
Fe
2+
/Fe
Fe
2+
+ 2e Fe
-0,440
Cr
3+
, Cr
2+
/ Pt
Cr
3+
+ e Cr
2+
-0,410
PbSO
4
, / Pb
PbSO
4
+ 2e Pb + SO
4
2-
-0,356
Co
2+
/ Co
Co
2+
+ 2e Co
-0,277
Ni
2+
/ Ni
Ni
2+
+ 2e Ni
-0,250
Sn
2+
/ Sn
Sn
2+
+ 2e Sn
-0,136
Pb
2+
/ Pb
Pb
2+
+ 2e Pb
-0,126
H
3
O
+
/ H
2
, Pt
2H
3
O+ + 2e H
2
+ 2H
2
O
0 (theo quy
c)
Cu
2+
, Cu
+
/ Pt
Cu
2+
+ e Cu
+
+ 0,153
Cu
2+
/ Cu
Cu
2+
+ 2e Cu
+ 0,337
OH
-
/ O
2
, Pt
1/2O
2
+ H
2
O + 2e 2OH-
+ 0,401
Cu
+
/ Cu
Cu
+
+ e Cu
+ 0,520
I
-
/ I
2
, Pt
I
2
+ 2e 2I
-
+ 0,536
Fe
3+
, Fe
2+
/ Pt
Fe
3+
+ e Fe
2+
+ 0,771
Hg
2
2+
/ Hg
Hg
2
2+
+ 2e 2Hg
+ 0,798
Ag
+
/ Ag
Ag
+
+ e Ag
+ 0,799
Hg
2+
/ Hg
Hg
2+
+ 2e Hg
+ 0,854
Hg
2+
, Hg
2
2+
/ Pt
2Hg
2+
+ 2e Hg
2
2+
+ 0,910
Br
-
/ Br
2
, Pt
Br
2
+ 2e 2Br
-
+ 1,066
Mn
2+
, H
3
O
+
/ MnO
2
,Pt
MnO
2
+ 4H
+
+ 2e Mn
2+
+ 2H
2
O
+ 1,236
76
Cl
2
O
7
2-
, Cr
3+
/ Pt
C
2
O
7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
+ 1,330
Cl
-
/ Cl
2
, Pt
Cl
2
+ 2e 2Cl
-
+ 1,359
Pb
2+
/ PbO
2
,Pb
PbO
2
+ 4H
+
+ 2e Pb
2+
+ 2H
2
O
+ 1,455
Au
3+
/ Au
Au
3+
+ 2e 2Au
+ 1,500
MnO
4
-
,H
3
O
+
,Mn
2+
/ Pt
MnO
4
-
, + 8H
+
+ 5e Mn
2+
+ 4H
2
O
+ 1,510
Ce
4+
,Ce
3+
/ Pt
Ce
4+
+ e Ce
3+
+ 1,610
Au
+
/ Au
Au
+
+ e Au
+ 1,700
F
-
/ F
2
,Pt
F
2
+ 2e 2F
-
+ 2,870
T nhn xet nay ta suy ra: ch nhng kim loai nao co th
in cc tiu chun nho hn 0 mi co kha nng y c
hiro ra khoi dung dch axit loang.
9.5. CHIU VA TRANG THAI CN BNG CUA PHAN NG
OXIHOA - KH
9.5.1. Chiu cua phan ng oxi hoa - kh
chng 4 ta a da vao cac d kin nhit ng
tnh s bin i entanpi t do cua phan ng va t kt
qua o co th kt lun v chiu phan ng. i vi phan
ng oxi hoa kh ta li dung mi lin h gia s bin i
entanpi t do va sut in ng cua phan ng xet
chiu cua no:
nFE G
T

. Phan ng oxi hoa kha ch co th
t xay ra khi: E > 0
Nhng S =
p
-
tr
,. Do o co th da vao th kh cua cac
cp oxi hoa - kha xet chiu phan ng oxi hoa - kh.
Thng xet chiu cua phan ng oxi hoa - kh trong dung
dch nc 25
0
C va vi muc ch khng cn chnh xac
cao trong dung dch u loang ta dung cng thc Nerst. y,
cn chu y rng theo cng c quc t, th
0
i
y la th
kh - ngha la cht tham gia trong phan ng in cc la
dang oxi hoa, con san phm la dang kh.
V du, i vi kim loai: M
n+
+ ne M. th cng thc
Nernst co dang:
[ ]
+
+
+ +
n
M M M M
M
n
n n
lg
059 , 0
0
/ /
Cht tham gia phan ng in cc trong dung dch nc,
ngoai cac cht oxi hoa ra con co th la H
3
O
+
va OH
-
.
V du: MnO
4
-
+ 5e + 8H
3
O
+
= Mn
2+
+ 12H
2
O
Th kh cua cp MnO
4
-
/Mn
2+
se la:
[ ][ ]
[ ]
+
+
+
+
2
8
3 4 0
/
lg
5
059 , 0
4
2
4
Mn
O H MnO
MnO Mn MnO
Trong trng hp in cc kh, v du: OH
-
/ O
2
,Pt vi
1/2O
2
+ H
2
O + 2e 2OH
-
[ ]
2
2 / 1
0
, ,
2
2 2
lg
2
059 , 0
+

OH
P
O
Pt O OH Pt O OH
V th kh cua cac cp phu thuc vao nng cac dang
va co th phu thuc vao pH cua dung dch nn chiu cua
77
phan ng oxi hoa - kh ngoai s phu thuc vao ban cht
cua cac cp con co th phu thuc vao nng cua cac
dang va pH cua mi trng.
9.5.2. Trang thai cn bng cua phan ng oxi hoa- kh
Khi cn bng cua phan ng oxi hoa - kh c thit lp:
G
T
= -nFE = 0
ngha la th cua hai cp tham gia phan ng oxi hoa - kh
bng nhau.
Da vao mi lin h:
0
T
G = -RTlnK = -nFE
0
, ta d dang
tnh c hng s cn bng cua cac phan ng oxi hoa -
kh khi bit th chun cua cac cp:
0
ln E K
nF
RT
hay:
059 , 0
.
lg
0
n E
K
Vi E
0
= (th kh chun cua cht oxi hoa) - (th
kh chun cua cht kh) trong phan ng khao sat va n la
s eleectron trao i trong phan ng.
9.6. S IN PHN
9.6.1. nh ngha
Ta hay xet hin tng khi nhung hai in cc graphit
c ni vi mt ngun in mt chiu vao mt dung
dch in li (v du dung dch CuCl
2
).
Di tac dung cua in trng, cac ion dng Cu
2+
i v
catt (cc m) thu thm hai electron bin thanh nguyn t
trung hoa: Cu
2+
+ 2e = Cu (s kh ion Cu
2+
), va cac ion Cl
-
i
v ant (cc dng) nhng hai electron bin thanh
nguyn t trung hoa: 2Cl
-
-2e = Cl
2
: (s oxi hoa ion Cl
-
).
Hin tng nh trn c goi la s in phn. Ban
cht cua s in phn la trn catt xay ra s kh va trn
ant xay ra s oxi hoa. Nhng cn chu y rng s oxi hoa
va s kh nay khng t xay ra nh trong pin ma chung ch
xay ra c la nh nng lng cua dong in.
Do o, co th nh ngha: in phn la qua trnh thc
hin phan ng oxihoa-kh trn b mt cac in cc khi
cho dong in mt chiu i qua dung dch cht in li hoc
qua cht in li nong chay, co kem theo s bin i in
nng thanh hoa nng.
9.6.2. S phn cc trong qua trnh in phn
Khi dong in i qua ranh gii phn chia in cc - dung
dch th trang thai in cua in cc (th cua no, mt
in cua lp in tch kep) se b thay i. Hin tng o
c goi la s phn cc in cc. Khi phn cc th
th cua in cc se khac vi th cn bng cua no (th
cua in cc khi khng co dong i qua). Khi xay ra s phn
cc, nu th cua in cc chuyn dch v pha dng
hn so vi th cn bng cua no th s phn cc c goi
la s phn cc ant, con ngc lai th c goi la s
phn cc catt.
78
Tuy thuc vao ban cht cua qua trnh lam bin i th
in cc ma ngi ta chia qua trnh phn cc ra thanh cac
loai khac nhau.
a. S phn cc nng : Phn cc nng sinh ra do
s bin i nng cua ion lp gn b mt in
cc. lp gn b mt ant, do kim loai b hoa tan, nng
ion tng do o theo cng thc Nernst th cua no se tng
(tr thanh dng hn). Trn catt xay ra s kh cation do o
nng cua no lp gn b mt giam i va th cua
in cc se giam i (tr thanh m hn).
Mt dong cang ln th s bin i nng cua cac
ion lp gn b mt in cc cang ln va do o s phn
cc in cc cang manh. lam giam s phn cc
nng ta phai khuy manh dung dch.
b. S phn cc hoa hoc: Khi dong in i qua ranh gii
phn chia in cc - dung dch co th xay ra phan ng gia
mi trng hoc cht in li vi vt liu lam in cc.
San phm sinh ra lam bin i tnh cht b mt in cc
va lam thay i th cua in cc. Hin tng o c
goi la s phn cc hoa hoc.
c. S phn cc in hoa: Ta quan sat th nghim sau:
Nhung hai in cc platin vao dung dch in li CuCl
2
chng
han, sau o ni hai in cc nay vi mt ngun in mt
chiu. B tr sao cho co th bin i lin tuc in ap t
vao mach.
Ban u, khi cha co in ap, th cua hai in cc d
nhin bng nhau. Khi bt u tng in ap, trong mach se co
mt dong in: electron se n catt (ni vi cc m cua
ngun in) va ri ant (ni vi cc dng cua ngun
in). Nhng electron t no khng i qua c dung dch
in li do o nu trn in cc khng xay ra qua trnh in
hoa th mt in cc se tch in m v d electron, con
mt in cc se tch in dng v thiu electron va cu
tao cua lp in tch kep se thay i ngha la xay ra s
phn cc in cc. Kt qua gia hai in cc sinh ra mt
hiu s in th co chiu ngc vi chiu cua ngun
in bn ngoai. Hin tng o c goi la s phn cc
in hoa.
9.6.3. Th phn huy va qua th
a. Th phn huy: Nh trn a noi, s in phn ch bt
u xay ra t mt in ap hoan toan xac nh. in ap ti
thiu gia hai in cc s in phan bt u xay ra
goi la th phn huy. Trong th nghim trn, phan ng in
cc: Cu
2+
+ 2e = Cu (trn catt)
2Cl
-
- 2e = Cl
2
(trn ant)
ch co th bt u xay ra khi th cua catoot m hn th cn
bng cua Cu
2+
|Cu va th cua cua ant dng hn th cua Cl
-
|Cl
2
. Th o c goi la th phong in cua ion.
79
Nh th v mt l thuyt, th phn huy cua mt cht
bng S.. cua pin tao bi cht thoat ra ant va catt.
b. Qua th: Trong nhiu trng hp, th phn huy thng
ln hn S.. cua pin tao bi cht thoat ra cac in cc.
Hiu s gia th phn huy va S.. cua pin tao bi cac
cht thoat ra trn cac in cc goi la qua th.
cac ion phong in c, th cua catt:
k k
+
'
va th
cua ant:
a a
+
'
. Trong o:
k
,
a
ln lt la th cn bng
cua cac cation va anion.
k
(
k
> 0) va
a
(
a
> 0) ln lt la
qua th trn catt va ant.
9.6.4. Qua trnh in phn cac cht
a. in phn cht in li nong chay
Cac cation i v catt va cac anion i v ant va phong
in. V du s in phn cua NaCl nong chay nh sau:
Catt NaCl ant
Na
+
+ e =Na Na
+
+ Cl
-
Cl
-
- e = Cl; 2Cl = Cl
2
Qua trnh in phn nong cahy thng c dung
iu ch cac kim loai Kim, Kim th, Nhm
b. in phn dung dch nc
Trong dung dch nc, khi thit lp mt in ap gia hai
in cc th catoin kim loai va H
3
O
+
i v pha catt va OH
-
i
v pha ant. Vn t ra la ion nao se phong in.
Qua trinh xay ra trn catt: Khi cho dong in i qua dung
dch, cation kim loai va H
3
O
+
tin gn ti b mt catt. Nu
th phong in cua cation dng hn th phong in cua
H
3
O
+
th cation kim loai se thu electron cua catt: M
n+
+ ne =
M . Trong trng hp ngc lai th H
3
O
+
se phong in:
H
3
O
+
+ e = H + H
2
O (va 2H = H
2
)
Qua trinh xay ra trn ant: Khi in phn dung dch nc
th t phong in cua cac anion nh sau: u tin la cac
anion khng cha oxi nh S
2-
, I
-
, Br
-
, Cl
-
... sau o n OH
-
va
cui cung la cac anion cha oxi nh NO
3
-
, SO
4
2-
, PO
4
3-
....
*************************************
80
MT S KIM TRA
THI MN HOA AI CNG - S 01
Cu 1: a) Trnh bay nguyn ly 2 cua nhit ng hoc:ni dung,
biu thc toan hoc
b) Tnh S trong qua trnh un nong 200g nc t 10
0
C
n 20
0
C ap sut khng i, bit C
P
(H
2
O) = 75,3J/mol..
Cu 2: Cho cp phn t sau: N
2
va N
2
+

. Cho Z
N
= 7
Vit cu hnh electron cua 2 phn t trn theo thuyt MO
va lp gian nng lng MO cua chung. So sanh bn
lin kt cua 2 phn t trn, giai thch.
Cu 3. Tnh hiu ng nhit cua phan ng 500
o
K va 1atm,
cho phan ng va cac s liu sau:
CH
3
OH(k) + 3/2 O
2
(k) = CO
2
(k) + 2 H
2
O (k)
H
o
298.
s (KJ/mol) -201,2 0 - 393,5 -241,8
C
p
(J/mol.) 49,4 29,4 37,1 33,6
Chp nhn C
0
P
thay i khng ang k trong khoang nhit
trn
Cu 4: Nhng mui nao trong nhng mui sau y b thuy
phn: KNO
3
, NaBr, NH
4
Cl, Na
2
SO
4
, (NH
4
)
2
CO
3
, FeCl
2
, Na
2
S,
Al
2
(SO
4
)
3
.Vit phng trnh thuy phn (nu xay ra)
Cu 5 . 445
0
C, phan ng pha kh: H
2
+ I
2
2HI co
hng s cn bng Kc = 50. Hoi nhit trn, nu un 1,27
g I
2
va 0,02 g H
2
th tao ra bao nhiu mol HI. Tnh s mol cua
tng kh trong hn hp cn bng tai nhit trn. Cho: I =
127, H = 1.
Cu 6: in ly la g? V sao trn thc t dung dch cht
in ly manh lai co in ly <1. Dung dch axit HCN 0,2M
co K
A
= 4,5.10
- 10
. Xac nh [H
3
O
+
] va in ly cua HCN.
Cu 7: a) 50
0
C, ap sut hi bao hoa cua dung dch cha 46 g
cht tan trong 250g C
2
H
5
OH la 207,2 mmHg. Xac nh khi
lng phn t M cua cht tan, bit nhit nay ap sut
hi bao hoa cua C
2
H
5
OH tinh khit la 219,8 mmHg.
b) Dung dch A cha etylenglycol va dung dch B cha
propylenglycol co nhit si bng nhau, cho bit dung dch
nao co nng C% ln hn, giai thch v sao?
o
K va 1atm,
CH
3
OH(k) + 3/2 O
2
(k) = CO
2
(k) + 2 H
2
O (k)
H
o
298
.s (kJ/mol) -201,2 0 - 393,5 -241,8
Cp (J/mol.) 49,4 29,4 37,1 33,6
Chp nhn C
0
P
trn
Cu 9: : Cho cac cht va cac dung dch sau: Ag , Ag
+
(10
-1
M) ;
Cu, Cu
2+
(10
- 2
M)
Hay ghep chung tao thanh mt pin, ve s va
vit ky hiu cua pin, cho bit chiu cua dong in. Tnh
81
sc in ng cua pin trn, cho bit:
0
(Ag+/Ag)
= 0,8V;
0
(Cu2+/Cu)
= 0,34V.
Cu 10: a) 1000
o
K hng s cn bng Kp cua phan ng:2SO
2
(k) + O
2
(k) 2SO
3
(k) bng 3,50 atm
-1
. Tnh ap sut ring luc
cn bng cua SO
2
va SO
3
nu ap sut chung cua h bng 1
atm va ap sut cn bng cua O
2
bng 0,1 atm.
b) Cho nhit hoa hi cua nc nguyn cht bng
2254,757 kJ/kg. Hoi di ap sut nao th nc se si 97
0
C.
****************************
Cu 1: a) Nguyn ly bt nh Heisenberg: ni dung, biu thc
toan hoc, y ngha
b) Cho nguyn t A co Z = 26. Hay vit cu hnh
electron cua ion A
3+
. Cho bit cac gia tr s lng t cua
electron ngoai cung cua ion A
3+
.
Cu 2: a) Giai phng trnh Sring thu c my s
lng t ? Hay cho bit y ngha cac s lng t o.
b) Vit cac gia tr n, l, m cua cac ham song cua mt
nguyn t A ng vi lp M ( n=3).
Cu 3 : a) 20
0
C phan ng : A E co vn tc phan ng la v,
mun vn tc phan ng tng 1024 phai tin hanh phan
ng nhit nao? Bit h s nhit cua phan ng
bng 2.
b) Phan ng phn huy H
2
O
2
nhit phong co nng
ban u cua H
2
O
2
la 0,4 mol/l, sau 5 phut con lai 0,2 mol/l,
hoi hng s tc cua phan ng la bao nhiu?
Cu 4: Cho tch s tan 25
0
C cua Ag
2
CO
3
la 6,2.10
- 12
, cua
Fe(OH)
3
la 27.10
- 36
. Tnh tan va nng cac ion do 2 cht
trn phn ly ra (g/l) trong dung dch bao hoa nhit trn.
Cho Ag = 108, C = 12 , O = 16 , Fe = 56 , H = 1.
Cu 5: Cho phan ng: CaCO
3
(r)

t
o
CaO(r) +
CO
2
(k)
- Vit biu thc tnh hng s cn bng K
P
.
- Tnh H
0
cua phan ng 1025
0
C bit:
CaCO
3
CaO + CO
2
H
0
298
.s (kJ/mol) -1206,87 - 635,09- 393,51
C
0
P
(J/mol.) 104,52 48,83 28,66
Chp nhn C
0
P
trn.
Cu 6: Tnh ap sut hi cua nc nguyn cht 20
0
C. Bit
nhit nay ap sut hi cua dung dch co 24 g ng
(sacaroz) tan trong 150g H
2
O la 17,39 mmHg.
Cho ng co M = 342.
Cu 7: a) Th phn huy la g? V mt ly thuyt no bng
ai lng nao?
82
b) Dung dch cha CuSO
4
va NaCl co nng (mol/l) nh
nhau (in cc tr, mang ngn xp, khi nc bt u b
in phn ca 2 in cc th dng lai). Vit phng trnh
in phn xay ra khi in phn. Mau sc quy tm thay i
th nao khi cho vao dung dch sau p.
Cu 8: a) in ly la g? No phu thuc vao cac yu t
nao?
b) Axit yu HA co nng 0,05M va hng s in ly
K=7.10
- 10
. Hay xac nh in ly va nng ion H
3
O
+
cua axit trong dung dch.
Cu 9: a) Trn ln hai dung dch HCl 0,1M va H
2
SO
4
0,1M vi
th tch bng nhau. Tnh pH cua dung dch thu c.
b)Tnh th kh cua cp Mn0
4
-
/Mn
2+
pH= 5,bit rng
[Mn0
4
-
] = 2[Mn
2+
] va E
0
Mn0
4
-
/Mn
2+

= 1,51V
Cu 10: Mt bnh phan ng cha 15 mol cht A va 18 mol
cht B c un nong n 600K th cn bng thit lp theo
phan ng: A + B 2C + 3D . Hn hp cn bng co ap
sut 1,43 atm va cha 10 mol cht C. Xac nh hng s cn
bng Kc va Kp cua phan ng tai nhit trn.
**********************
Cu 1: a) Cho bit hnh dang cac am my :3p
z
, 3d
xy
, cac
am my lai hoa sp
2
,sp
3
. Ch ro s nh hng cua cac am
my trong khng gian .
b) Nu iu kin lai hoa bn. Trong mt chu ky, khi i
t u n cui chu ky th kha nng lai hoa tng hay giam,
v sao?
Cu 2: Cho nguyn t A co Z= 8.
a. Hay giai thch cac trang thai hoa tr co th co cua A theo
thuyt hoa tr spin.
b. Hay ve cu hnh e cua phn t A
2
theo thuyt MO. Tnh
s lin kt trong phn tu va cho bit tnh cht t cua no.
Cu 3: Th nao la hin tng thm thu, ap sut thm
thu? trnh bay nh lut Vanhp v ap sut thm
thu.Vit cng thc tnh ap sut thm thu.
Cu 4: Tnh hng s cn bng K
P
i vi phan ng:
a) N
2
+ 3H
2
2NH
3

b) 1/2N
2
+ 3/2H
2
NH
3
25
0
C va ap sut 1atm bit : G
0
298
.s (NH
3
) = -16,64 kJ/mol.
Cu 5: Khi hoa tan 32g CuSO
4
khan vao nc, nhit lng
thoat ra la 3,16Kcal. Khi hoa tan 50 g CuSO
4
.5H
2
O vao nc thu
nhit lng la 0,56Kcal. Xac nh nhit hyrat hoa CuSO
4
khan. Cho Cu = 64 , S = 32 , O= 16 , H = 1.
Cu 6: a) Tnh in ly cua dung dch HCN 0,2M bit hng
s in ly cua HCN la 7,2.10
- 10
.
83
b) Dung dch cua 1,6 g NaOH tan trong 100g H
2
O ng c
-1,414
0
C, hng s nghim ng cua H
2
O la 1,86. Tnh h
s Vanhp i
Cu 7: a) Quy tc pha Gibbs va y ngha cua no.
b) Cho phan ng: 2NOCl = 2NO + Cl
2
co nng lng
hoat hoa E* = 100 kJ/mol 350
0
K hng s tc K = 8.10
- 6
l/mol.giy. Tnh hng s tc 400
0
K.
Cu 8: Cho phan ng sau: KMnO
4
+ KNO
2
+ H
2
O MnO
2
+
KNO
3
+ KOH
Cn bng phan ng trn theo phng phap ion- in t va
vit phng trnh Nec cho cac cp xy hoa - kh . Tnh ng
lng khi cua KMnO
4
va KNO
2
.
Cu 9: Tnh S
0
298
; H
0
298
; G
0
298
cua phan ng sau:
CaCO
3

t
CaO + CO
2
H
0
298,
s (kJ/mol) -1206,9 - 635,1 - 393,5
S
0
298
(J/mol.) 92,9 38,1 213,7
Hay cho bit phan ng co xay ra iu kin trn khng,
tai sao?
Cu 10: Ngi ta ch tao mt pin Daniell vi: [Ag
+
] = 0,18M;
[Zn
2+
] = 0.3M.
Hay ve s cu tao, vit ky hiu cua pin, vit cac
phng trnh phan ng in cc va phng trnh tng
cng trong pin . Xac nh sc in ng cua pin bit:
0
(Zn2+/Zn)
= - 0,76V ;
0
(Ag+/Ag)
= 0,80V.
********************************
84
Cu 1: a) Oxy hoa hoan toan 0,235g nguyn t M thu c
0,40g xt MO. Hay tnh ng lng cua M, bit ng
lng cua oxy bng 8.
b) Cho phan ng: Al
2
(SO
4
)
3
+ 6NaOH = 2Al(OH)
3
+
3Na
2
SO
4
2
(SO
4
)
3
. Cho Al = 27, S =
32, O =16.
Cu 2: Ve gian nng lng cac MO cua: O
2
, O
2
-
, O
2
+
. T o
so sanh bn va ch ra tnh cht thun t hay nghch t
cua chung. Cho Z
O
= 8
Cu 3 : t chay 7,8 gam benzen long 25
0
C, 1atm tao ra
kh CO
2
va H
2
O long toa ra mt nhit lng bng 326,7 kJ.
Xac nh nhit sinh cua benzen long iu kin a cho v
nhit va ap sut. Bit nhit sinh 25
0
C cua CO
2
(k);
H
2
O(l) tng ng bng - 393,5 kJ/mol va - 285,8 kJ/mol.
Cu 4: Tnh hng s baz K
CH3COO-
cua dung dch: CH
3
COONa
0,1M bit pH = 8,9
Cu 5: a) Trnh bay 3 ni dung c ban cua thuyt lin kt
cng hoa tr (Thuyt VB).
b) Tnh hng s cn bng cua phan ng: Sn
2+
+
2Fe
3+
Sn
4+
+ 2Fe
2+
Cho
0
(Fe3+/Fe2+)
= + 0,77V;
0
(Sn4+/Sn2+)
= + 0,15V.
Cu 6: Hay trnh bay cac yu t anh hng n vn tc
cua phan ng hoa hoc: nng , nhit , xuc tac
Cu 7: Xet phan ng: 2 SO
2
(k) + O
2
(k) 2 SO
3
(k)
a) Vit phng trnh vn tc (phng trnh ng hoc) cua
phan ng. Tc phan ng thay i th nao khi V bnh
giam 3 ln?
b) Khi nng cac cht ban u la [SO
2
] = [O
2
] = 1,0.10
- 4
mol/l th vn tc ban u cua phan ng la 2,8.10
- 6
mol/l.giy.
Tnh hng s vn tc k cua phan ng.
Cu 8: a) Tch s tan la g? Cho bit iu kin tao kt tua
va hoa tan kt tua (Co v du minh hoa)
b) Xac nh pH cua dung dch Ni(OH)
2
bao hoa 25
0
C
.
Bit Ni(OH)
2
la cht in ly t tan va tch s tan cua no
25
0
C la 1,3.10
-16
.
Cu 9: Cho phan ng: C(gr) + O
2
(k) = CO
2
(k)
a) Vit biu thc tnh hng s cn bng K
p
.
b) Tnh H
0
cua phan ng tai 1500
0
K bit:
Cht C(gr) O
2
(k) CO
2
(k)
H
0
298
.s (kJ/mol) - 393,51
C
0
P
(J/mol.) 8,64 29,36 37,13
Chp nhn C
0
P
trn.
Cu 10: a/ Pha la g? Vit biu thc toan hoc cua quy tc
pha.
85
b/ Tnh s pha, s bc t do cua h thu c khi cho
40g KNO
3
vao 200g H
2
O tai 10
0
C bit tan (tai 10
0
C) cua
KNO
3
la 21,2g/100g H
2
O.
Cho C = 12, O = 16, H = 1, N = 14, K = 39
********************************
86
I HC NNG CNG HA X HI CH NGHA VIT
NAM
Trng HSP-Khoa Ha c lp - T do - Hnh phc
THI MN HOA AI CNG - Ln 1
(Thi gian lm bi: 60 pht)
Cu 1: Trnh bay nguyn ly 2 cua nhit ng hoc:ni dung,
biu thc toan hoc
Cu 2: Cho cp phn t sau: N
2
va N
2
+

. Cho Z
N
= 7
Vit cu hnh electron cua 2 phn t trn theo thuyt MO
va lp gian nng lng MO cua chung. So sanh bn
lin kt cua 2 phn t trn, giai thch.
o
K va 1atm,
CH
3
OH(k) + 3/2 O
2
(k) = CO
2
(k) + 2 H
2
O (k)
H
o
298.
s (KJ/mol) -201,2 0 - 393,5 -241,8
C
p
(J/mol.) 49,4 29,4 37,1 33,6
Chp nhn C
0
P
trn
Cu 4: Nhng mui nao trong nhng mui sau y b thuy
phn: KNO
3
, NaBr, NH
4
Cl, Na
2
SO
4
, (NH
4
)
2
CO
3
, FeCl
2
, Na
2
S,
Al
2
(SO
4
)
3
.Vit phng trnh thuy phn (nu xay ra)
Cu 5 . 445
0
C, phan ng pha kh: H
2
+ I
2
2HI co
hng s cn bng Kc = 50. Hoi nhit trn, nu un 1,27
g I
2
va 0,02 g H
2
th tao ra bao nhiu mol HI. Tnh s mol cua
tng kh trong hn hp cn bng tai nhit trn. Cho: I =
127, H = 1.
Cu 6: in ly la g? V sao trn thc t dung dch cht
in ly manh lai co in ly <1.
Cu 7: 50
0
C, ap sut hi bao hoa cua dung dch cha 46 g
cht tan trong 250g C
2
H
5
OH la 207,2 mmHg. Xac nh khi
lng phn t M cua cht tan, bit nhit nay ap sut
hi bao hoa cua C
2
H
5
OH tinh khit la 219,8 mmHg.
o
K va 1atm,
CH
3
OH(k) + 3/2 O
2
(k) = CO
2
(k) + 2 H
2
O (k)
H
o
298
.s (kJ/mol) -201,2 0 - 393,5 -241,8
Cp (J/mol.) 49,4 29,4 37,1 33,6
Chp nhn C
0
P
trn
Cu 9: : Cho cac cht va cac dung dch sau: Ag , Ag
+
(10
-1
M) ;
Cu, Cu
2+
(10
- 2
M)
87
Hay ghep chung tao thanh mt pin, ve s va
vit ky hiu cua pin, cho bit chiu cua dong in. Tnh
sc in ng cua pin trn, cho bit:
0
(Ag+/Ag)
= 0,8V;
0
(Cu2+/Cu)
= 0,34V.
Cu 10: 1000
o
K hng s cn bng Kp cua phan ng:2SO
2
(k)
+ O
2
(k) 2SO
3
(k) bng 3,50 atm
-1
. Tnh ap sut ring luc cn
bng cua SO
2
va SO
3
nu ap sut chung cua h bng 1 atm
va ap sut cn bng cua O
2
bng 0,1 atm.
****************************
88
I HC NNG CNG HA X HI CH NGHA VIT NAM
Cu 1: Cho nguyn t A co Z = 26. Hay vit cu hnh electron
cua ion A
3+
. Cho bit cac gia tr s lng t cua electron
ngoai cung cua ion A
3+
.
Cu 2: Giai phng trnh Sring thu c my s lng
t ? Hay cho bit y ngha cac s lng t o.
Cu 3 : 20
0
C phan ng : A E co vn tc phan ng la v,
mun vn tc phan ng tng 1024 phai tin hanh phan
ng nhit nao? Bit h s nhit cua phan ng
bng 2.
Cu 4: Phan ng phn huy H
2
O
2
nhit phong co nng
ban u cua H
2
O
2
la 0,4 mol/l, sau 5 phut con lai 0,2 mol/l,
hoi hng s tc cua phan ng la bao nhiu?
Cu 5 : Cho tch s tan 25
0
C cua Ag
2
CO
3
la 6,2.10
- 12
, cua
Fe(OH)
3
la 27.10
- 36
. Tnh tan va nng cac ion do 2 cht
trn phn ly ra (g/l) trong dung dch bao hoa nhit trn.
Cho Ag = 108, C = 12 , O = 16 , Fe = 56 , H = 1.
Cu 6 : Cho phan ng: CaCO
3
(r)

t
o
CaO(r) +
CO
2
(k)
+ Vit biu thc tnh hng s cn bng K
P
.
+ Tnh H
0
cua phan ng 1025
0
C bit:
CaCO
3
CaO + CO
2
H
0
298
.s (kJ/mol) -1206,87 - 635,09 - 393,51
C
0
P
(J/mol.) 104,52 48,83 28,66
Chp nhn C
0
P
trn.
Cu 7 : Tnh ap sut hi cua nc nguyn cht 20
0
C. Bit
nhit nay ap sut hi cua dung dch co 24 g ng
(sacaroz) tan trong 150g H
2
O la 17,39 mmHg. Cho ng co M =
342.
Cu 8 : Dung dch cha CuSO
4
va NaCl co nng (mol/l) nh
nhau (in cc tr, mang ngn xp, khi nc bt u b
in phn ca 2 in cc th dng lai). Vit phng trnh
in phn xay ra khi in phn. Mau sc quy tm thay i
th nao khi cho vao dung dch sau p.
Cu 9 : in ly la g? No phu thuc vao cac yu t nao?
Cu 10 : Trn ln hai dung dch HCl 0,1M va H
2
SO
4
0,1M vi th
tch bng nhau. Tnh pH cua dung dch thu c.
89
**********************
90
Cu 1: Cho bit hnh dang cac am my :3p
z
, 3d
xy
, cac am
my lai hoa sp
2
,sp
3
. Ch ro s nh hng cua cac am my
trong khng gian .
Cu 2: Cho nguyn t A co Z= 8.
Vit cu hnh e v giai thch cac trang thai hoa tr co th co
cua A theo thuyt hoa tr spin.
Cu 3: Th nao la hin tng thm thu, ap sut thm
thu? trnh bay nh lut Vanhp v ap sut thm
thu.Vit cng thc tnh ap sut thm thu.
Cu 4: Tnh hng s cn bng K
P
i vi phan ng:
a) N
2
+ 3H
2
2NH
3

b) 1/2N
2
+ 3/2H
2
NH
3
25
0
C va ap sut 1atm bit : G
0
298
.s (NH
3
) = -16,64 kJ/mol.
Cu 5: Khi hoa tan 32g CuSO
4
khan vao nc, nhit lng
thoat ra la 3,16Kcal. Khi hoa tan 50 g CuSO
4
.5H
2
O vao nc thu
nhit lng la 0,56Kcal. Xac nh nhit hyrat hoa CuSO
4
khan. Cho Cu = 64 , S = 32 , O= 16 , H = 1.
Cu 6: Dung dch cua 1,6 g NaOH tan trong 100g H
2
O ng c
-1,414
0
C, hng s nghim ng cua H
2
O la 1,86. Tnh h s
Vanhp i
Cu 7: Cho phan ng: 2NOCl = 2NO + Cl
2
co nng lng hoat
hoa E* = 100 kJ/mol 350
0
K hng s tc K = 8.10
- 6
l/mol.giy. Tnh hng s tc 400
0
K.
Cu 8: Cho phan ng sau: KMnO
4
+ KNO
2
+ H
2
O MnO
2
+
KNO
3
+ KOH
Cn bng phan ng trn theo phng phap ion- in t va
vit phng trnh Nec cho cac cp xy hoa - kh . Tnh ng
lng khi cua KMnO
4
va KNO
2
.
Cu 9: Tnh S
0
298
; H
0
298
; G
0
298
cua phan ng sau:
CaCO
3

t
CaO + CO
2
H
0
298,
s (kJ/mol) -1206,9 - 635,1 - 393,5
S
0
298
(J/mol.) 92,9 38,1 213,7
Hay cho bit phan ng co xay ra iu kin trn khng,
tai sao?
Cu 10: Ngi ta ch tao mt pin Daniell vi: [Ag
+
] = 0,18M;
[Zn
2+
] = 0.3M.
Hay ve s cu tao, vit ky hiu cua pin, vit cac
phng trnh phan ng in cc va phng trnh tng
91
cng trong pin . Xac nh sc in ng cua pin bit:
0
(Zn2+/Zn)
= - 0,76V ;
0
(Ag+/Ag)
= 0,80V.
********************************
92
Cu 1: Cho phan ng: Al
2
(SO
4
)
3
+ 6NaOH = 2Al(OH)
3
+
3Na
2
SO
4
2
(SO
4
)
3
. Cho Al = 27, S =
32, O =16.
Cu 2: Vit cu hnh e ca nguyn t Oxi. Cho Z
O
= 8
Cu 3 : t chay 7,8 gam benzen long 25
0
C, 1atm tao ra
kh CO
2
va H
2
O long toa ra mt nhit lng bng 326,7 kJ.
Xac nh nhit sinh cua benzen long iu kin a cho v
nhit va ap sut. Bit nhit sinh 25
0
C cua CO
2
(k);
H
2
O(l) tng ng bng - 393,5 kJ/mol va - 285,8 kJ/mol.
Cu 4: Trnh by nguyn l 1 ca nhit ng hc: ni dung, biu thc ton hc,
ngha.
Cu 0 5 . Cho phn ng: N
2
(k) + 3H
2
(k) 2NH
3
(k)
Tnh hng s cn bng K
P
ti 25
0
C v p sut 1atm bit G
0
298
(NH
3
) = - 16,64
kJ/mol. Gi tr K
P
thay i nh th no khi phn ng trn vit di dng:
2
1
N
2
(k) +
2
3
H
2
(k) NH
3
(k).
Cu 6: Hay trnh bay cac yu t anh hng n vn tc
cua phan ng hoa hoc: nng , nhit , xuc tac
Cu 7: Xet phan ng: 2 SO
2
(k) + O
2
(k) 2 SO
3
(k)
Vit phng trnh vn tc (phng trnh ng hoc) cua
phan ng. Tc phan ng thay i th nao khi V bnh
giam 3 ln?
Cu 8 : Cho phan ng: 2 SO
2
(k) + O
2
(k) 2 SO
3
(k)
Khi nng cac cht ban u la [SO
2
] = [O
2
] = 1,0.10
- 4
mol/l th vn tc ban u cua phan ng la 2,8.10
- 6
mol/l.giy. Tnh hng s vn tc k cua phan ng.
Cu 8: Tch s tan la g? Cho bit iu kin tao kt tua va
hoa tan kt tua (Co v du minh hoa)
Cu 9: Cho phan ng: C(gr) + O
2
(k) = CO
2
(k)
c) Vit biu thc tnh hng s cn bng K
p
.
d) Tnh H
0
cua phan ng tai 1500
0
K bit:
Cht C(gr) O
2
(k) CO
2
(k)
H
0
298
.s (kJ/mol) - 393,51
C
0
P
(J/mol.) 8,64 29,36 37,13
Chp nhn C
0
P
trn.
93
Cu 10 : Tnh hng s cn bng cua phan ng: Sn
2+
+ 2Fe
3+
Sn
4+
+ 2Fe
2+
Cho
0
(Fe3+/Fe2+)
= + 0,77V;
0
(Sn4+/Sn2+)
= + 0,15V.
********************************
94
AP AN S 01
Cu 1: a)Nguyn l 2 cua nhit ng hoc:
-Tn tai mt ham trang thai goi la entropi, ky hiu S. dS la
vi phn toan phn.
- Gia s co mt bin i thun nghch v cung nho trong
o h trao i vi mi trng nhit T mt lng
nhit Q
t
th dS = (Q
t
/T)(J/K,Cal/K)
Biu thc toan hoc:dS (Q/T) hay S tch phn t 1 n 2
cua (Q/T)
Y ngha:(SGK)
b/ S = Cp.ln(T
2
/T
1
) = (200/18).75,3.ln(293/283).
Cu 2:
Phn t N
2
Ion N
2
+
bi= 3 bi = 5/2
( T vit cu hnh in t theo s trn) bn
lin kt: N
2
> N
2
+
Cu 3. Hng dn: (Vi T
0
= 298; T = 500 K)
H
0
298
= H
0
298cui
- H
0
298u
= [- 393,5 + 2.(- 241,8)] - (-
201,2) = - 675,9 (kJ/mol)
Cp = Cp cui - Cp u = (37,1 + 2.33,6) - (49,4 + 3/2. 29,4)
= 10,8 (J/mol.K)
Cu 4: Hng dn:
NH
4
Cl + H
2
O NH
4
OH + HCl (NH
4
)
2
CO
3
+ H
2
O
NH
4
OH + NH
4
HCO
3
FeCl
2
+ H
2
O HCl + FeOCl Al
2
(SO
4
)
3
+ 6 H
2
O
2Al(OH)
3
+ 3 H
2
SO
4
Na
2
S + H
2
O = NaHS + NaOH
Cu 5 . Hng dn:
Ta c: nH
2
= 0,02/2 = 0,01 mol v nI
2
= 1,27/(2.127) =
0,005 mol
H
2
+ I
2
2HI
Ban u 0,01 0,005 0
Cn bng (0,01-n/2) (0,005-n/2)
Hng s cn bng Kc l: K
C
= [HI]
2
/ [H
2
].[I
2
] = 50
95
mol / kJ -673,7 .dT .10 8 , 10 675,9 - dT . C H H
3 -
T
T
T
T
P
298
0
T
0
0 0
+ +

Gii ra c n
HI
= 9,34.10
-3
mol
( ti cn bng) n
H2
= 5,33.10
-3
mol, n
I2
= 3,3.10
-4
mol
Cu 6: Hng dn:
in ly la t s gia s phn t phn li trn s phn
t hoa tan:
tan hoa phn t S
li phn phn t S

0 < < 1
Trong thc t, vi cht in li manh, in li lun
lun nho 1 v dn in ng lng cua dung dch cht
in ly manh pha loang bt k cung u nho hn
dn in ng lng v cung nn = /

< 1
Ta co K =
1
. 2 , 0
1
2 2
C
= 4,5.10
-10

2
+ 22,5.10
-10
- 22,5.10
-10
= 0
5.10
-5
[H
3
O
+
] = 5.10
-5
.0,2 = 10
-5
Chu y: V K <10
-5
nnco th dung cng thc = (K/C)
1/2
va [H
+
]
= .C cung cho kt qua = 4,7.10
-5
=> nh vy [H
3
O
+
] =
4,7.10
-5
.0,2 = 0,94.10
-5
Cu 7: Hng dn:a. P/P
0
= N
B
= [n
B
/(n
A
+n
B
)]
((219,8-207,2)/219,8)=(46/M)/((250/46)+(46/M)) M =
147,7 .V.C
b. V T
S
= k
S
. = k
S
.m/M Vi C% = [m/
(m+1000)].100
M(propylenglycol) = 76; M(etilenglicol)= 62
Vi cung T
S
va k
S
th M m c Vy C%(ddA) < C%(ddB).
Cu 8. Hng dan: (Vi T
0
= 298; T = 500 K)
H
0
298
= H
0
298cui
- H
0
298u
= [ - 393,5 + 2.(- 241,8) ]- (-
201,2) = - 675,9 (kJ/mol)
Cp = Cp cui - Cp u = (37,1 + 2.33,6) - (49,4 + 3/2. 29,4)
= 10,8 (J/mol.K)
Cu 9: : Hng dn:
K hiu cua pin: Cu|Cu
2+
||Ag
+
|Ag
Cu
2+
/Cu =
0
+ (0,059/2)lg(10)
-2
= 0,34 - 0,059;
96
Cu
2+
Ag
+
Ag
Cu
e
i
mol / kJ -673,7 .dT .10 8 , 10 675,9 - dT . C H H
3 -
T
T
T
T
P
298
0
T
0
0 0
+ +

Ag
+
/Ag =
0
+ (0,059/1)lg(10)
-1
= 0,8 - 0,059; => E = 0,46V
Cu 10: Hng dn:
a) Goi X la ap sut cua SO
2
th ap sut ring cua SO
3
la:
1 - P
O2
- X = 0,9 - X;
5 , 3
1 , 0 .
) 9 , 0 (
.
2
2
2
2 2
3

X
X
P P
P
Kp
O SO
SO
Giai ra c: x
= 0,57atm; P
SO3
= 0,33 atm.
b)Ta co:
)
1 1
(
. 303 , 2
) lg(
1 2 1
2
T T R
H
P
P

P
2
= 683,6 mmHg
AP AN S 02
Cu 1: Hng dn: a. Nguyn ly bt nh Heisenberg:
- Khng th xac nh chnh xac, ng thi ca vn tc va
toa cua vi hat vt cht chuyn ng.Nu mt vt
chuyn ng theo phng x vi bt nh cua toa x
va bt nh cua vn tc la V
x
th h thc: V
x
. x >
h/m (h : hng s Planck; m : khi lng cua vt)
- Theo h thc ny ta thy vic o toa cua vt
cang chnh xac bao nhiu th vic o vn tc cua no cang
kem chnh xac by nhiu va ngc lai. Khng ve c quy
ao chuyn ng hat vi m.
b. A (Z = 26) : 1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
3d
5
A
3+
: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5

Cac s lng t cua in t ngoai cung : n = 3 , l = 2, m =
2, m
s
= + 1/2
Cu 2: Hng dn:
a) Giai phng trnh Sring thu c 3 s lng t:
- S lng t chnh: n = 1, 2, 3...
Xac nh nng lng E
n
cua e trong nguyn t:
E
n
= -(1/n
2
).(m.Z.
2
e
4
/8.
0
2
.h
2
)= -13,6.Z
2
/n
2
(eV/ng)
Vi H co Z = 1th E
n
= -(1/n
2
).(m.Z.
2
e
4
/8.
0
2
.h
2
)= -(13,6/n
2
)(eV)
Ky hiu n: 1 2 3 4 5 6 7 ....
Mc En : K L M N O P Q ...
- Slng t phu l = 0, 1, 2, ...n-1
Xac nh ln cua mmen ng lng orbital.
|M|=(l(l+1))
1/2
.(h/2)
Nhng e ng vi cung mt mc nmg lng E
n
co th
co n gia tr khac nhau cua |M|Ky hiu: l = 0 1
2 3 ...
Trang thai s p d f ...
- s lng t t m = 0, t1, t2,..., tl. Xac nh hnh
chiu mmen ng lng orbital ln truc Z: M
Z
=
m.h/2.
97

b) Gia tr n, l, m cua ham song cua nguyn t A ng vi lp
M la:

(300)
,
(31-1)
,
(310)
,
(31+1)
,
(32-2)
,
(32-1)
,
(320)
,
(32+1)
,
(32+2)
.
Cu 3 : Hng dn:
a) Goi T la nhit cn th 2
((T-293)/10)
= 1024. Vy T = 393
0
K la
120
0
C.
b) Phan ng H
2
O
2
H
2
O + 1/2 O
2
la bc nht.
(- dC/dt) = k.(C
0
- Ct). (dCt/C
0
-Ct)= kdt
k= (1/t).(ln(C
0
/(C
0
-Ct))) = (1/5).(ln(0,4/(0,4-0,2))) k= 0,32
Cu 4: Hng dn: Ag
2
CO
3
2Ag
+
+ CO
3
2-
s 2s s T
1
= (2s)
2
.s = 6,2.10
-12

s = 10
-4
(1,55)
1/3

M = 1,157.10
-4
M
[Ag
+
] = 1,157.10
-4
.2.108 g/l ; [CO
3
2-
] = 1,157.10
-4
.60 g/l
tan cua Ag
2
CO
3
= 1,157.10
-4
.276

g/l
Fe(OH)
3
Fe
3+
+ 3 OH
-
s s 3s T
2
= b.(3b)
3
= 27.10
-36
b =
10
-9
M
[Fe
3+
] = 56.10
-9
g/l; [OH
-
] = 51.10
-9
g/l
tan cua Fe(OH)
3
= 107. 10
-9
g/l
Cu 5: Hng dn:
Ta co:K
P
= P
CO2
; H
o
= 178270 (J) ; C
P
= -27,03 (J/)
H
T
= H
o
+C
P
.T = 178270 - 27,03.(1298 - 298) = 151,20 kJ
Cu 6: Hng dn:
Ta co:
3
10 . 4 , 8
18
150
342
24
342
24
o
P
P
P
0
= 17,54 mmHg
Cu 7: Hng dn:
Th phn huy la in ap ti thiu gia 2 in cc
s in phn bt u xay ra.
V mt l thuyt, th phn huy cua mt cht bng
S cua pin tao bi cht thoat ra Anot va Catot.
CuSO
4
+ 2NaCl Cu + Cl
2
+ Na
2
SO
4
CuSO
4
+ H
2
O Cu + 1/2O
2
+ H
2
SO
4
dung dch sau in phn co H
2
SO
4
Qu tm hoa o.
Cu 8: Hng dn:
a. in ly: SGK.
b. Ap dung cng thc:
1
2
C
K
a

10
2
10 . 140
1

C
K
a

2
+ 140.10
-10
- 140.10
-10
= 0 = 1,18.10
-4
[H
3
O
+
] = 0,05.1,18.10
-4
= 5,9.10
-6
M
Chu y: V K < 10
-5
1/2
va
[H
+
] = .C (kt qua nh vy)
Cu 9. Hng dn:
a) [H
+
] = (1/2).(0,1+ 0,2)=0,15 pH = -lg[H
+
] = 0,83
b) tai pH = 5 th [H
+
] = 10
-5

M
98

T
=
T
0
+ (0,059/n).lg(([MnO
4
-
].[H
+
]
8
)/[Mn
2+
]) = 1,51 +
(0,059/n)lg(10
-5
)
8
= 1,038 V
[MnO
4
-
+ 5e
-
+ 8H
+
= Mn
2+
+ 4H
2
O]
Cu 10: Hng dn:
A + B =2C + 3D n = 3
Cn bng (15-x/2) (18-x/2) x 3x/2 Vi x = 10(mol)
Ta c: 10 13 10 15
Tng s mol lc cn bng: 10 + 13 + 10 + 15 = 48.
Hng s cn bng: K
N
= [(10/48)
2
.15/48)
3
] / [ (10/48).(13/48)] =
0,0235
Kp = K
N
.P
n
= 0,0235. 1,43
3
= 0,069 ; K
C
= K
P
/(RT)
n
= 0,069/
(0,082.600)
3
= 5.10
7
.
**********************************
AP AN S 03
Cu 1: Hng dn:
a. Cac hnh ve tng ng(hinh ve)
Sp
2
: tao ra 3 my e hng v 3 nh cua hnh tam
giac u
Sp
3
: tao ra 4 my e hng v 4 nh cua hnh t
din u.
b. iu kin lai hoa bn: Cac orbital lai hoa co nng
lng xp x nhau, mt xen phu phai u ln, mt
in tch u ln.
trong mt chu k, i t u n cui chu k, kha nng
lai hoa giam,v cac mc nng lng ns, np cang cui chu ky
cang xa nhau.
Cu 2: Hng dn:
a/ A co Z=6 la 1s
2
2s
2
2p
4
. Hoa tr la 2.
b/ Cu hnh e cua phn t A
2
theo thuyt MO. S lin
kt trong phn tu la 2 va cht co tnh cht thun t .
Cu 3: Hng dn:
Hin tng thm thu: SGK
Ap sut thm thu: la ap lc cn tac dung ln dung dch
ngng s thm thu.
99
nh lut: i vi dung dch loang, ap sut thm thu cua
dung dch co c bng ap sut ma cht hoa tan co c
nu no dang kh cung nhit vi dung dch va chim
th tch bng th tch cua dung dch. Cng thc: RT
M
m
pv
Cu 4: Hng dn:
G
0
298pu
= 2.-16,64=-33,28 kj Thay R=8,314 ,T=298. Ta co: K
p
=
exp(
RT
G
) = 6.8.10
5
Nu phng trnh c vit di dang: 1/2 N
2
+ 3/2 H
2

NH
3
K
/
P
= [NH
3
]/[N
2
]
1/2
.[H
2
]
3/2
= [K
P
]
1/2
= 825
Cu 5. Hng dn:
32g CuSO
4
(0,2 mol) H
2
O: Q = Q
tan
+ Q
hidrat
= -3,16Kcal
50g CuSO
4
.5H
2
O (0,2 mol) H
2
O: Q
tan
= 0,56 Kcal
Q
hidrat
= Q - Q
tan
= - 3,72 Kcal
Nhit hidrat hoa CuSO
4
khan la - 3,72 /0,2 = -18,6 Kcal/mol
Cu 6: Hng dn:
a.Ta co K =
1
. 2 , 0
1
2 2
C
= 7,2.10
-10

2
+ 36.10
-10
- 36.10
-10
= 0
= 5,9.10
-5
Chu y: V K < 10
-5
1/2
cung
cho kt qua nh vy
b. Ta co C (nng molan) = 0,4
t
l thuyt
= K
.C = 1,86.0,4 = 0,744 va H s Vanthoff i =

9 , 1
744 , 0
414 , 1
Cu 7: Hng dn:
a)Quy tc pha: C = K - + 2: s bc t do bng s cu t
tr s pha cng hai.
b) lg(kT
2
/kT
1
)= (E/2,303R)(1/T
1
- 1/T
2
)
lg(k400/8.10
-6
)= (10
5
/2,303.8,314).(1/350 - 1/400) k400 =
5,9.10
-4
lit/mol.giy.
Cu 8: Hng dn:
MnO
4
-
+ 3e + 2H
2
O = MnO
2
+ 4OH
-

T
=
0
+
(0,059/3).lg([MnO
4
-
]/[OH
-
]
4
)
NO
2
-
- 2e + H
2
O = NO
3
-
+ 2H
+

T
=
0
+
(0,059/2).lg([NO
3
-
].[H
+
]
2
/[NO
2
-
])
=> 2KMnO
4
+ 3KNO
2
+ H
2
O = 2 MnO
2
+ 3KNO
3
+ 2KOH.
=> KMnO
4
= 2.158/6 = 52,67; KNO
2
= 3.85/6 = 42,5
Cu 9: Hng dn:
S
o
= (213,7 + 38,1) - 92,9 = 158,9 (J/)
H
o
= (-635,1 - 393,5) - (-1206,9) = 178,3 (kJ)
G
o
= 178,3 - 298.158,9.10
-3
= 130,9 (kJ)
G > 0 phan ng khng xay ra 25
o
C, 1 atm.
Cu 10: Hng dn:
100
Ky hiu cua pin: Zn | Zn
2+
|| Ag
+
| Ag
Cac phan ng trong pin:
Zn - 2e Zn
2+
(trn in cc kem) vaAg
+
+ e Ag
(trn in cc bac)
Zn
2+
/Zn =
0
+ (0,059/2)lg(3.10
-2
) = 0,775 v
Ag
+
/Ag =
0
+ (0,059/1)lg(18.10
-2
) = 0,65 v
E = 1,425 V
*************************************
101
Zn
2+
Ag
+
Ag
Zn
e
i
AP AN S 04
Cu 1: Hng dn:
a. Ta co m
oxi phan ng
= 04, - 0,235 = 0,165 (g);
M
/
O
=
2,35/1,65
M
= 11,4
b.
Al2(SO4)3
=
6
3 . 96 2 . 27 +
= 57
Cu 2: Hng dn: bn lin kt: O
2
-
< O
2
< O
2
+
do:
Phn t O
2
Ion O
2
-

Ion O
2
+
bi = 2 bi = 3/2
bi = 5/2
thun t thun t
thun t
Cu 3: Hng dn: C
6
H
6
+
2
15
O
2
6CO
2
+ 3 H
2
O
Q
sinh(CO2)
= -393,5 (kJ/mol); Q
sinh(H2O)
= -285,8 (kJ/mol)
H
0
= 6. Q
S (CO2)
+ 3.Q
S(H2O)
- Q
S(c6H6)
Q
S (C6H6)
= 48,6 (kJ/mol)
Cu 4: Hng dn:
CH
3
COOH CH
3
COO
-
+ H
+
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-
pH = 8,9 pOH = 5,1 x = [OH
-
] = 7,5.10
-6
CH
3
COO
-
thuy phn x
x
x
K
B
1 . 0
2
= 5,7.10
-10
Cu 5: Hng dn:
a) 3 ni dung c ban cua thuyt lin kt cng hoa tr
(Thuyt VB), cho v du
b) Ta co:
o
Sn Sn
o
Fe Fe
E E E
+ + + +

2 4 2 3
/ /
= 0,77 - 0,15 = 0,62V
lnK = nFE/RT lgK = nE
o
/0,059 = 21 => k = 10
21
Cu 6: Hng dn:
Nng :p/ ng th( nh lut tac dung khi
lng); p/ d th( cht rn khng co mt trong pt ng
hoc cua p/)
Nhit : quy tc Van
0
hoff ; phng trnh Arrhenius
102
Xuc tac: Cht xuc tac, xuc tac ng th(c ch- hp
cht trng gian) , xuc tac d th (c ch - thuyt hp phu) ,
xuc tac men (cac enzim),tnh chon loc cua xuc tac
Cu 7: Hng dn:
a. P.t ng hoc: v = k.[SO
2
]
2
.[O
2
]. V V giam 3 ln C
M
tng
3 ln v
2
= 27.v
1
b. [SO
2
] = [O
2
] = 10
-4
M => v = k.[SO
2
]
2
.[O
2
] k = 2,8.10
6
Cu 8: Hng dn:
a) Trong dung dch bao hoa cua cht in li t tan, tich s
nng cua cac ion la mt hng s. Hng s o c
goi la tch s tan, ky hiu la T.
-k tao kt tua: tch s nng cac ion ln hn tch s
tan cua cht in li t tan.
-k hoa tan kt tua : tch s nng cac ion nho hn tch
s tan cua cht in li t tan.
VD: T
SrSO4
= 3,6.10
-7
. Nu [Sr
2+
][SO
4
2-
]>3,6.10
7-
th co kt tua xay
ra.
b) [Ni
2+
][OH
-
]
2
= 1,3.10
-16
[OH
-
] = (1,3.10
-16
/4)
1/3
pH = 14 +
lg[OH
-
]= 8,85
Cu 9: Hng dn: K
P
=
2
2
O
CO
P
P
=>C
P
= 37,13 - ( 8,64 + 29,36 ) =
- 0,87 (J/mol.)
H
o
T
= H
o
298
+C
P
.T=-393,51+[-0,87.10
-3
.(1500 - 298)] =
-394,555 kJ/mol
Cu 10: Hng dn:
a)Pha: SGK . Biu thc toan hoc quy tc pha Gibbs:C = K -
+ 2
Vi C: bc t do; K: S cu t c lp; : S pha.
b) Ta co: KNO
3
tan ht. Vy,h co 1pha long ,2 Cu t
c lp (H
2
O & KNO
3
)
s bc t do C = 2 - 1 + 2 = 3
********************************
103
CU HI V BI TP HA I
CNG
(Dng cho cc lp va hc va lm)
TS.GVC. Trn Mnh Lc khoa Ha HSP HN
CHNG 1: KHI NIM C BN TRONG HA HC
Cu 01. Tnh ng lng ca Fe v axit trong cc phn ng ha tan Fe bng dung
dch HCl, dung dch HNO
3
(cho kh NO).
Cu 02. Tnh ng lng ca Ba(OH)
2
v H
3
PO
4
trong phn ng ca Ba(OH)
2
vi
H
3
PO
4
.
Cu 03. Oxi ha hon ton 0,235 g Mg bng oxi thu c 0,4 g MgO. Tnh ng
lng ca Mg , bit ng lng ca oxi bng 8.
Cu 04. Ha tan hon ton 1,12 g kim loi M bng dung dch HNO
3
long thu c
0,448 lt kh NO (ktc). Tnh ng lng ca M trong phn ng trn.
Cu 05. Tnh ng lng ca cc cht tham gia trong cc phn ng sau:
a. NaOH + H
2
SO
4
= Na
2
SO
4
+ H
2
O
b. CaCO
3
+ HCl = CaCl
2
+ CO
2
+ H
2
O
CHNG 2: CU TO NGUYN T V HTTH
Cu 06. Hm sng l g? V sao trng thi chuyn ng ca e trong nguyn t li c
m t bng hm sng (ph thuc ta v thi gian).
Cu 07. Trng thi ca in t trong nguyn t c c trng bng my s lng t?
Vit hm sng ca e cui cng trong nguyn t ca nguyn t c Z = 11.
Cu 08. Hy vit cu hnh e ca nguyn t A (Z
A
= 7) theo cng thc ch v cng
thc lng t. Vit hm sng v tnh nng lng (b qua hiu ng chn), momen
ng lng, hnh chiu ca mmen ng lng trn trc Z, mmen ng lng spin
v chiu ca mmen ng lng spin trn trc Z i vi e cui cng.
Cu 09. Vit cu hnh e ca nguyn t A c Z
A
= 17. Cho bit v tr ca A trong h
thng tun hon (STT, chu k, nhm), tnh cht ha hc c trng, s oxihoa dng v
m cc i, cng thc ca oxt bc cao A
x
O
y
, hidrua bc cao AH
z
.
Cu 10. Ion X
3+
c cu hnh e lp ngoi cng l 2p
6
. Vit cu hnh e ca X v cho bit
v tr ca X trong h thng tun hon (STT, chu k, nhm), tnh cht ha hc c trng,
s oxihoa dng v m cc i, cng thc ca oxt bc cao X
x
O
y
, hidrua bc cao XH
z
.
CHNG 3: LIN KT HA HC V CU TO PHN T
104
Cu 11. Trnh by cc c trng c bn ca lin kt, cho v d minh ha. Lin kt gia
2 nguyn t khi no l lin kt ion, khi no l lin kt cng ha tr v khi no l lin
kt cho-nhn?
Cu 12. Trnh by cc c im c bn ca lin kt ion v hp cht ion, ca lin kt
cng ha tr v hp cht cng ha tr.
Cu 13. Trnh by cc lun im c bn ca thuyt cng ha tr (thuyt VB). Hy gii
thch cc trng thi ha tr c th c ca nguyn t A (Z
A
= 6) theo thuyt ha tr spin.
Cu 14. Gia cc AO s v AO p (trong cng mt lp ca cng 1 nguyn t) c th c
nhng dng lai ha no (ch r s nh hng khng gian vi tng trng hp, minh
ha bng hnh v ng vi nguyn t C trong cc phn t C
2
H
2
, C
2
H
4
, CH
4
).
Cu 15. Vit phng trnh trng thi ca kh l tng v ca kh thc, gii thch s
khc bit gia chng. iu kin no th phng trnh trng thi ca kh l tng p
dng c cho kh thc.
CHNG 4: CC NGUYN L CA NHIT NG HC
Cu 16. Trnh by nguyn l 1 ca nhit ng hc: ni dung, biu thc ton hc,
ngha.
Cu 17. Trnh by nh lut Hecx v cc h qu.
Cu 18. Nhit dung l g? Vit biu thc xc nh nhit dung, nhit dung mol ng p
v nhit dung mol ng tch.
Cu 19. Trnh by nguyn l 2 ca nhit ng hc: ni dung, biu thc ton hc,
ngha.
Cu 20. Xc nh bin thin entropi (Tnh S
0
) trong qu trnh dn n ng nhit
thun nghch 1 mol kh l tng t th tch V
1
n th tch V
2
= 10V
1
ti 27
0
C (R = 2
cal/mol.) v trong qu trnh un nng 200 g nc t 10
0
C n 20
0
C p sut khng
i, bit C
P
(H
2
O) = 75,3 J/mol..
CHNG 5: CC HM NHIT NG
Cu 21 Cho phn ng sau: CO(k) + 1/2O
2
(k) = CO
2
(k)
Tnh H
0
ca phn ng trn ti 398
0
K, bit H
0
298
= - 67,64 kcal/mol:
Cho C
P
(CO) = 6,97; C
P
(O
2
) = 7,05, C
P
(CO
2
) = 8,96.(cal/mol.)
Chp nhn C
P
thay i khng ng k trong khong nhit trn.
Cu 22. Cho phn ng sau: C(gr) + O
2
(k) CO
2
(k).
H
0
298,S
(kJ/mol): - 393,51
Cho C
P
(J/mol.): 8,64 29,36 37,13
Tnh H
0
0
K. Chp nhn C
P
thay i khng ng k
trong khong nhit trn.
Cu 23. Cho phn ng vi cc gi tr nhit ng:
C
2
H
2
(k) + H
2
O(h) C
2
H
5
OH(h)
G
0
298
(kJ/mol): 68,12 - 228,59 - 168,6
S
0
298
(J/mol.): 219,45 188,7 282,0
Tnh H
0
298
v vit phng trnh nhit ha ca phn ng trn.
Fe
2
O
3
(r) + 3H
2
(k) 2Fe(r) +3H
2
O(h)
Cht: Fe
2
O
3
(r) 3H
2
(k) 2Fe(r) 3H
2
O(h)
H
0
298,S
(Cal/mol): - 196,300 -57800
S
0
298
(Cal/mol.): 20,9 31,2 6,5 45,1
105
Xc nh chiu ca phn ng v nhit ti thiu phn ng t xy ra (so vi
iu kin tiu chun), gi s trong khong nhit S, H khng ph thuc vo
nhit .
Cu 25. Ngi ta sn xut kh than kh bng phn ng (vi cc gi tr nhit ng):
C(graphit) + H
2
O(h) CO(k) + H
2
O(h)
H
0
298,S
(Cal/mol): - 57,8 - 26,4
S
0
298
(Cal/mol.): 1,36 45,1 47,3 31,2
Xc nh chiu ca phn ng 727
0
C, gi s trong khong nhit S, H
khng ph thuc vo nhit .
CHNG 6: NG HA HC
Cu 26. Cho phn ng A + 2B = C c hng s vn tc l k = 0,4. Nng ban u ca
A l 0,4M, ca B l 0,7M. Tnh vn tc ca phn ng lc ban u v vn tc ca phn
ng ti thi im t khi nng ca A cn li l 0,1M.
Cu 27. Phn ng tng hp NH
3
xy ra ti nhit khng i:
2NO(k) + O
2
(k) 2NO
2
(k)
a. Vit phng trnh ng hc ca phn ng. Tc phn ng thay i th no
khi p sut tng ln 3 ln.
b. Khi nng ban u ca cc cht l: C
NO
= C
O2
= 1,0.10
-4
mol/lt th vn tc ban
u ca phn ng l 2,8.10
-6
mol/lt.giy. Tnh hng s vn tc k ca phn ng.
Cu 28. 20
0
C phn ng A E c vn tc l v, mun vn tc phn ng tng ln
1024 ln th phi tin hnh phn ng nhit no? Bit h s nhit ca phn ng
bng 2.
Cu 29. Khi tng nhit ca 1 phn ng thm 50
0
C th vn tc ca n tng ln 1200
ln. Vy h s nhit ca phn ng l bao nhiu?.
Cu 30. 150
0
C mt phn ng (c h s nhit l 3) xy ra v kt thc trong 16
pht.
a. Mun phn ng xy ra v kt thc trong 10 giy th phi tin hnh phn ng
nhit bao nhiu.
a. Xc nh thi gian xy ra v kt thc ca phn ng trn khi tin hnh 200
0
C.
CHNG 7: CN BNG HA HC
Cu 31. iu kin xc nh, phn ng tng hp NH
3
t c cn bng vi nng
cn bng ca cc cht l: [N
2
] = 3M, [H
2
] = 9M, [NH
3
] = 4M. Xc nh nng ban
u ca N
2
v H
2
v tnh hng s cn bng ca phn ng: N
2
(k) + 3H
2
(k) 2NH
3
(k).
Cu 32. Cho cc gi tr nhit ng ca phn ng sau:
N
2
(k) + 3H
2
(k) 2NH
3
(k).
H
0
298,S
(kJ/mol): - 46,19
S
0
298
(J/mol.): 191,49 130,59 192,51
Tnh hng s cn bng K
P
, K
C
, K
N
ca phn ng ti 25
o
C.
Cu 33. Cho phn ng: N
2
(k) + 3H
2
(k) 2NH
3
(k)
Tnh hng s cn bng K
P
ti 25
0
0
298
(NH
3
) = - 16,64
kJ/mol. Gi tr K
P
thay i nh th no khi phn ng trn vit di dng:
2
1
N
2
(k) +
2
3
H
2
(k) NH
3
(k).
Cho nhn xt v lin h gia K
P
v cch vit phng trnh phn ng.
106
4HCl(k) + O
2
(k) 2Cl
2
(K) + 2H
2
O(k)
H
0
298,S
(kJ/mol): -92,31 -241,83
S
0
298
(J/mol.): 186,7 205,03 222,9 188,7
Tnh hng s cn bng K
P
v vit phng trnh nhit ha ca phn ng ti 298
0
K.
b. Mun tng hiu sut oxiha HCl th nn tin hnh phn ng p cao hay thp?.
Cu 35. Cho phn ng xy ra trong bnh kn nhit khng i: A + 2B C
Khi t trng thi cn bng, nng cc cht C
A
= 0,6M, C
B
= 1,2M, C
C
=
2,16M. Nu thm vo trong h mt lng cht B th sau mt thi gian h t trng thi
cn bng mi c nng C
C
= 2,3 M. Tnh lng cht B thm vo trong h.
CHNG 8: DUNG DCH LONG CHT KHNG IN LY
Cu 36. Xc nh nng phn trm, nng mol/lit, nng ng lng, nng
molan v nng phn s mol ca dung dch thu c khi ha tan 9,2 gam ru etylic
v 200 gam nc. Chp nhn t trng ca dung dch thu c l 1.
Cu 37. ha tan ca 1 mui 80
0
C bng 64,7 v 17
0
C bng 13,8. Mun iu ch
1kg mui ny nguyn cht bng cch kt tinh li mui ny t dung dch bo ha
80
0
C h xung 17
0
C th cn ly bao nhiu mui rn (cha 2% tp cht) v nc.
Cu 38. Xc nh khi lng phn t ca mt cht tan khng in ly, bit rng 80
0
C
p sut hi ca dung dch cha 3,09g cht ny trong 370g ietylete l 643,6 mmHg,
cn p sut hi ca ietylete nguyn cht 80
0
C l 647,9mmHg.
Cu 39. Khi ha tan 3,142g lu hunh vo 40 gam benzen, nhit si ca dung dch
tng thm 0,81
0
C so vi nhit si ca benzen nguyn cht(p sut kh quyn khng
i). Xc nh cng thc phn t ca lu hunh, bit hng s nghim si ca benzen l
2,64.
Cu 40. Tnh p sut thm thu ca dung dch cha 3,1g anilin (C
6
H
5
NH
2
) trong 1 lt
nc 21
0
C. Mun c dung dch HCHO cng c p sut thm thu nh vy th cn
phi phi ha tan bao nhiu gam HCHO vo 1 lt nc.
CHNG 9: DUNG DCH CHT IN LY
Cu 41. Cho cc gi tr nhit ng ca hp cht v ion sau:
Cht: KOH K
+
.(aq) OH
(aq)
H
0
298,S
(KCal/mol): - 101,8 - 60,3 - 54,97
S
0
298
(Cal/mol.): 14,2 24,2 - 2,57
Hy chng t KOH l cht in ly mnh nhit phng (25
0
C)
Cu 42. C 2 dung dch cha cng mt lng dung mi (nc) v ng c cng
mt nhit . Dung dch th nht cha 0,5 mol ng saccaroz, dung dch th hai
cha 0,2 mol CaCl
2
. Xc nh in ly biu kin ca CaCl
2
trong dung dch th 2.
Cu 43. Cho 100ml dung dch cha hn hp HCl 0,1M v H
2
SO
4
0,05M vo 400ml
dung dch cha hn hp NaOH 0,1M v Ba(OH)
2
0,05M. Tnh pH ca dung dch thu
c sau phn ng.
Cu 44. Tch s tan l g? Cho bit iu kin kt ta v ha tan kt ta? Cho v d
minh ha. Tch s tan ca Fe(OH)
3
25
0
C l 2,7.10
-35
. Tnh tan v nng cc ion
trong dung dch bo ha ca n ti 25
0
C.
Cu 45. Tnh xem c kt ta CaSO
4
hay khng nu cho 2 th tch bng nhau ca 2
dung dch CaCl
2
v Na
2
SO
4
cng c nng 0,01M. Tch s tan T
CaSO4
= 2,3.10
-4
.
CHNG 10: CC QU TRNH IN HA HC
107
Cu 46. Nu nguyn tc bin i ha nng thnh in nng. Cho bit cc qu trnh xy
ra trn cc in cc khi pin lm vic v qu trnh in phn.
Cu 47. Cho phn ng sau: KMnO
4
+ KNO
2
+ H
2
O MnO
2
+ KNO
3
+ KOH
Cn bng phn ng theo phng php ion in t v vit phng trnh Nernst
cho cc cp oxihoa-kh.
Cu 48. Cho hai in cc: Ag Ag
+
(10
-1
M) v Cu Cu
2+
(10
-2
M)
Hy ghp 2 in cc li thnh 1 pin, v s cu to v vit k hiu ca pin, cho
bit chiu ca dng in v chiu chuyn di ca dng in t. Tnh sc in ng ca
pin ti 25
o
C, bit
o
Ag+/Ag
= 0,80V,
o
Cu2+/Cu
= 0,34V.
Cu 49. Mt pin cu to t 2 in cc u bng Zn t vo cc dung dch ZnSO
4
c
nng ln lt l 0,5M v 0,05M. Sc in ng ca pin 25
o
C l 0,018V v
in li biu kin ca ZnSO
4
c nng 0,05M l 35%. Vit k hiu ca pin v tnh
in li biu kin ca ZnSO
4
c nng 0,5M.
Cu 50. in phn dung dch cha CuSO
4
v NaCl c nng (mol/lt) bng nhau
(in cc tr, c mng ngn xp) n khi nc bt u b in phn c 2 in cc th
dng li. Vit phng trnh xy ra ti cc in cc v phng trnh khi in phn. Mu
sc qu tm thay i nh th no khi cho vo dung dch sau in phn..
======================
108
TRNG HSP-KHOA HA c lp - T do - Hnh phc
KIM TRA MN HA I CNG
NM HC 2008 - 2009
Mn hc:
HA I CNG
S n v hc phn: 03.
Gio vin ra :
TS. TRN MNH LUC.
Khoa Ha-Trng HSP-N
Duyt
S 01 (Thi gian lm bi: 90 pht)
109
Cu 01. Tnh ng lng ca Fe v axit trong cc phn ng ha tan Fe bng dung dch
H
2
SO
4
long v dung dch H
2
SO
4
c, nng.
Cu 02. Trng thi ca in t trong nguyn t c c trng bng my s lng t?
Vit cu hnh in t v hm sng ca e cui cng ca nguyn t c Z = 5.
Cu 03. Trnh by cc lun im c bn ca thuyt cng ha tr (thuyt VB). Hy gii
thch cc trng thi ha tr c th c ca nguyn t A (Z
A
= 6) theo thuyt ha tr spin.
Cu 04. Trnh by nguyn l 1 ca nhit ng hc: ni dung, biu thc ton hc, ngha.
Cu 05. Cho phn ng sau: C(gr) + O
2
(k) = CO
2
(k).
H
0
298,S
(kJ/mol): - 393,51
Cho C
P
(J/mol.): 8,64 29,36 37,13
Tnh H
0
0
K. Chp nhn C
P
thay i khng ng k
trong khong nhit trn.
Cu 06. Phn ng tng hp NH
3
xy ra ti nhit khng i:
2NO

k) + O
2
(k) 2NO
2
(k)
a. Vit phng trnh ng hc ca phn ng. Tc phn ng thay i th no khi
p sut tng ln 2 ln.
b. Khi nng ban u ca cc cht l: C
NO
= C
O2
= 1,0.10
-4
mol/lt th vn tc ban u
ca phn ng l 2,8.10
-6
mol/lt.giy. Tnh hng s vn tc k ca phn ng.
Cu 07. Cho phn ng: N
2
(k) + 3H
2
(k) 2NH
3
(k)
Tnh hng s cn bng K
P
ti 25
0
0
298
(NH
3
) = - 16,64
kJ/mol. Gi tr K
P
thay i nh th no khi vit phn ng dng:
2
1
N
2
(k) +
2
3
H
2
(k) NH
3
(k).
Cho nhn xt v lin h gia K
P
v cch vit phng trnh phn ng.
Cu 08. Xc nh khi lng phn t ca mt cht tan khng in ly, bit rng 80
0
C p
sut hi ca dung dch cha 3,09g cht ny trong 370g ietylete [C
2
H
5
OC
2
H
5
] l 643,6
mmHg, cn p sut hi ca ietylete nguyn cht 80
0
C l 647,9 mmHg.
Cu 09. Cho 100ml dung dch cha hn hp HCl 0,1M v H
2
SO
4
0,05M vo 400ml dung
dch cha hn hp NaOH 0,1M v Ba(OH)
2
0,05M. Tnh pH ca dung dch thu c sau
phn ng.
Cu 10. Cho hai in cc: Ag nhng trong dung dch AgNO
3
0,1M v Cu nhng trong
dung dch Cu(NO
3
)
2
0,01M. Hy ghp 2 in cc li thnh 1 pin, v s cu to v vit
k hiu ca pin, cho bit chiu ca dng in v chiu chuyn di ca dng in t khi pin
hot ng. Tnh sc in ng ca pin ti 25
o
C, bit
o
Ag+/Ag
= 0,80V,
o
Cu2+/Cu
= 0,34V.
------------------------------------------------------------------------------------------------------------
Cho: Fe = 56, H = 1, C = 12, O = 16, S = 32, R = 8,314(J/mol.)
TRNG HSP-KHOA HA c lp - T do - Hnh phc
KIM TRA MN HA I CNG
NM HC 2008 - 2009
Mn hc:
HA I CNG
S n v hc phn: 03.
Gio vin ra :
TS. TRN MNH LUC.
Khoa Ha-Trng HSP-N
Duyt
110
S 02 (Thi gian lm bi: 90 pht)
Cu 01. Ha tan hon ton 1,12 g kim loi M bng dung dch HNO
3
long thu c 0,448
lt kh NO (ktc). Tnh ng lng ca M trong phn ng trn.
Cu 02. Vit cu hnh e ca nguyn t A c Z
A
= 17. Cho bit v tr ca A trong h thng
tun hon (STT, chu k, nhm), tnh cht ha hc c trng, s oxihoa dng v m cc
i, cng thc ca oxt bc cao A
x
O
y
, hidrua bc cao AH
z
.
Cu 03. Gia cc AO s v AO p (trong cng mt lp ca cng 1 nguyn t) c th c
nhng dng lai ha no (ch r s nh hng khng gian vi tng trng hp, minh ha
bng hnh v ng vi nguyn t C trong cc phn t C
2
H
2
, C
2
H
4
, CH
4
).
Cu 04. Nhit dung l g? Vit biu thc xc nh nhit dung, nhit dung mol ng p v
nhit dung mol ng tch.
C
2
H
2
(k) + H
2
O(h) C
2
H
5
OH(h)
G
0
298
(kJ/mol): 68,12 - 228,59 - 168,6
S
0
298
(J/mol.): 219,45 188,7 282,0
Tnh H
0
298
v vit phng trnh nhit ha ca phn ng trn.
Cu 06. 20
0
C phn ng A E c vn tc l v
1
. Nu tin hnh phn ng 120
o
C th
vn tc phn ng l v
2
tng ln bao nhiu ln so vi v
1
, bit h s nhit ca phn ng
bng 2.
N
2
(k) + 3H
2
(k) 2NH
3
(k).
H
0
298,S
(kJ/mol): - 46,19
S
0
298
(J/mol.): 191,49 130,59 192,51
Tnh hng s cn bng K
P
, K
C
, ca phn ng ti 25
o
C.
Cu 08. Khi ha tan 3,142g lu hunh vo 40 gam benzen, nhit si ca dung dch tng
thm 0,81
0
C so vi nhit si ca benzen nguyn cht (p sut kh quyn khng i).
Xc nh cng thc phn t ca lu hunh (hng s nghim si ca benzen l 2,64).
Cu 09. Tnh xem c kt ta CaSO
4
hay khng nu cho 2 th tch bng nhau ca 2 dung
dch Ca(NO
3
)
2
nng 0,001M v Na
2
SO
4
nng 0,1M. Tch s tan T
CaSO4
= 2,3.10
-4
.
Cu 10. in phn dung dch cha x mol CuSO
4
v 3x mol NaCl (in cc tr, c mng
ngn xp) n khi nc bt u b in phn c 2 in cc th dng li. Vit phng
trnh xy ra ti cc in cc v phng trnh in phn. Mu sc qu tm thay i nh th
no khi cho vo dung dch sau in phn.
------------------------------------------------------------------------------------------------------------
Cho: Fe = 56, H = 1, C = 12, O = 16, S = 32, N = 14, R = 8,314(J/mol.)
111

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CHNG 1

MT S KHAI NIM C BAN CUA HOA

CU HOI VA BAI TP CHNG 1

la hng s in mi cua chn khng, m la khi

, trong o n = 1, 2, 3, ... va c goi la

. (dU: vi phn toan phn;

ngha la trong trng hp nay co

. Nh vy, n v cua entropi la

Phi hp hai nguyn l 1 va 2 ta co: dU TdS - pdV + W

ln lt la ap sut ring phn cua A, B, E, D

ch phu thuc va nhit nn i vi mt phan ng a

6.3. S CHUYN DCH CN BNG

nng phn mol cua i.

la nhng h s ty l ch phu thuc vao ban cht

= 1,86, con dung mi khng

cua mt cht co mt gia tr

.C = 1,86.0,4 = 0,744 va H s Vanthoff i =

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