Solutions

Chng 11
CN BNG TRONG DUNG DCH LNG

Solutions
Khi nim v h phn tn v dung dch
- H phn tn:
+ Mt cht l ht rt nh c phn b vo trong cht kia.


+ Phn loi:
H phn tn th (h l lng): d >100m huyn ph.
nh tng.
H phn tn cao (h keo): 1m < d < 100m
H phn tn phn t - ion (dung dch thc): d < 1m
cht phn tn mi trng phn tn.
Solutions
Dung mi
Mi trng phn tn
Cht tan
Cht phn tn
Dung dch
S TO THNH DUNG DCH
Solutions
DUNG DCH- l h ng th bn nhit ng, gm khng t
hn hai cht trng thi phn tn phn t v thnh phn c
th bin thin lin tc trong gii hn xc nh
Dung dch kh
* Khng kh
Dung dch rn
* Thu tinh (Na
2
O, CaO tan trong SiO
2
)
*Vng tan trong bc
Dung dch lng
*Dung dch nc ng(ng(r) +H
2
O dung dch)
*Dung dch H
2
SO
4
(SO
3
(k) + H
2
O dung dch)

*Ru Voka (C
2
H
5
OH (l) + H
2
O dung dch)
Solutions
DUNG DCH LNG
C ch to thnh dd lng
Qu trnh vt l qu trnh chuyn pha
Qu trnh ho hc -qu trnh solvat ho
tng tc gia cht tan v dung mi

Solvat ho vt l
Solvat ho ho hc
AH
sol
<0 , AS
sol
<0
EOS
Tng tc gia tiu
phn v cht tan l
yu t hng u
quyt nh s to
thnh dd
AH
cp
,AS
cp
Solutions
Tng tc ht gia
cht tan v dung mi
cng mnh th qu
trnh ho tan cng
thun li
V d - ethanol tan tt trong nc
Ethanol = CH
3
CH
2
OH
Lc tng tc=lin kt hydro;lng cc-lng cc; khuch tn
Solutions

Glucose
c lin kt hydro nn
tan rt tt trong nc.

Cyclohexane
ch c lc khuch tn
khng tan trong nc.
Solutions
Vitamin A tan trong dung mi khng cc (cht bo)
Vitamin C tan trong nc.
Solutions
Vitamin no
tan trong
nc v
vitamin no
tan trong
cht bo?
Solutions
QU TRNH HO TAN V CN BNG HO TAN
Cht tan (r) + dung mi Dung dch
Ho tan
Kt tinh
bh
C
C
ln RT
K
Q
ln RT G = = A
Dung dch bo ho AG=0 c = c
bh
= tan
Dd cha bo ha AG < 0 c < c
bh

Dd qu bo ho AG > 0 c > c
bh


Cn bng
Solutions
Khi nim v tan S
tan - nng ca cht tan trong dd bo ha
TAN
CC DUNG DCH BO HO 20
0
C v 50
0
C
CHT TAN
Solutions
Cht tan l cht rn
S- thng biu din s gam cht tan tan ti a
trong100g dung mi
S > 10g - cht d tan
S < 1g - cht kh tan
S < 0,01g- cht gn nh khng tan

TAN CA CC HALOGENUA KIM LOI KIM TRONG H
2
O
TAN (s gam mui/100g dung mi)
Solutions
Cht tan l cht kh
S- thng biu din bng s ml kh (tan ti a)
tan trong 100g dung mi hoc 100ml dung mi
Cht tan l cht in ly kh tan
S thng biu din bng s mol cht in ly
kh tan (tan ti a) trong 1lit dung dch
Solutions
14.2
tan ca mt s ion thng dng trong nc
TAN KHNG TAN
Ngai tr
Ngai tr
Ngai tr
Solutions
CC YU T NH HNG N TAN
Bn cht ca dung mi v cht tan
Nhit , p sut
Mi trng
Solutions
Cc hp cht c cc tan tt trong dung
mi c cc hn l dung mi khng cc
phn
cc ca
dung mi
NaCl th :
Tan tt trong nc
Tan t trong ethyl alcohol
Khng tan trong ether v benzene
NH HNG CA BN CHT CHT TAN
V DUNG MI
Cht tng t tan trong cht tng t.

Solutions
Cc cht khng cc th tan tt trong
dung mi khng cc hn l cc dung
mi c cc.
phn
cc ca
dung mi
Benzene th
Khng tan trong nc
Tan trong ether.
Solutions
nh hng ca nhit v p sut
Kh + dung mi dung dch
AH
cp
<0 AH
s
<0
AH
ht
< 0
AG= 0 P
tan S
P
S
K
ht
=
T khng i, p
sut ring phn
ca kh tng S
tng

nh lut
Henry
Solutions


EOS
T tng tan cht
kh gim
Kh + dung mi dung dch

AH
ht
<0
Solutions
Cht rn + dung mi dung dch AH
ht

p sut hu nh khng nh hng n tan ca cht rn
k bnh thng.
AH
ht
< 0
Tth S

AH
ht
>0
Tth S

Khong 95%
hp cht ion c
tan tng theo
nhit .
Solutions
S THAY I TNH CHT NHIT NG
KHI TO THNH DUNG DCH
AG
ht
=AH
ht
-TAS
ht

Kh +dm(l) = dung dch(l)
AH
ht
=AH
cp
(-)+AH
sol
(-)


-
<0
AS
ht
= AS
cp
(-) + AS
sol
(-)
<0
Rn + dm(l) = dung dch (l)
AH
ht
=AH
cp
(+)+AH
sol
(-)

<0 hay>0
AS
ht
= AS
cp
(+) + AS
sol
(-) >0
Solutions
DUNG DCH L TNG
L dung dch c AH
ht
=0 ; AV
ht
=0 ; AU
ht
=0
Trong dung dch lc tng tc gia cc tiu phn
cng loi v khc loi ging nhau.S to thnh dd l
do s tng entropy.
Tnh cht ca dd l tng khng ph thuc vo bn
cht cht tan m ph thuc vo nng ca chng.
Dd lng t kh tt k l tng l dd m cc cu t
ca n c cu to phn t v nhng thuc tnh vt l
v ho hc ging nhau hoc rt gn nhau:
Hn hp cc ng phn quang hc.
Dd cc cu t ch khc nhau v thnh phn ng v
V d - H
2
O + D
2
O
Dd nhng cht ng ng cnh nhau
V d - Benzen + toluen ; hexan +heptan

Solutions
Nu lc tng tc gia cht tan v dung mi mnh hn
lc tng tc gia cc tiu phn cng loi th dd ny
thng c AH
ht
<0 , AV
ht
<0.
Dung dch thc
Ngc li, nu lc tng tc gia cht tan v dung mi
yu hn lc tng tc gia cc tiu phn cng loi th dd
ny thng c AH
ht
>0 , AV
ht
>0
Loi dd ny thng xy ra cho h m c hai cu t u c
cc.Tng tc ht gia chng c th dn ti cc qu trnh
ho hc (solvat ho, to lk hydro, to hp cht ho hc )
V d - h nc v axit nitric

Loi dd ny thng xy ra cho h m
c hai cu t c tnh phn cc khc
nhau r rt V d- ho tan cht c cc
vo dm khng cc: aceton trong CS
2

Solutions
EOS
Thu nhit
Dd l tng
To nhit
Tng tc
dm-ch tan
mnh hn
Tng tc
dm-ch tan
yu hn
Solutions
Dung dch thc
Ethanol v nc c lc
tng tc gia chng
mnh hn gia cc
ethanol vi nhau v gia
cc pt nc vi nhau.
Nn khi trn 50 mL H
2
O
+ 50 mL C
2
H
5
OH th th
tch nh hn 100 mL
EOS
Solutions
Nng dung dch
a. Nng phn trm:
% 100
m
m
% C
i
i
=

b. Nng mol:
c. Nng molan:
dm g 1000
n
C
ct
m
=
d. Nng phn mol:

=
i
i
i
n
n
N
e. Nng ng lng:
C
N -
s ng lng gam cht tan / 1lit dd
dd ml 1000
n
C
ct
M
=
Solutions
P SUT HI BO HO CA CHT LNG
NGUYN CHT

Lng Hi
Bay hi AH > 0
Ngng t AH < 0

T, AG = 0
Cn bng pha
K
p
= (P)
cb
= P
0

p sut hi bo ho ca cht lng l hng s
nhit xc nh v tng theo nhit

P
cb
=P
0
(T)
Solutions
Gin trng thi
V . T
H
dT
dP
A
A
=
L H ; R H ; R
L
Phng trnh Clapeyron Clausius
Solutions
Nhit si ca bt c pha lng no (nguyn cht
hay dung dch) cng u bt u si nhit m
ti p sut hi bo ho ca n bng p sut
ngoi.
i vi cht lng nguyn cht, khi p sut ngai
khng i,nhit si khng thay i trong sut qu
trnh si cho n khi ton b cht lng chuyn ht
thnh hi.
Solutions
Nhit ng c ca bt c pha lng no
(nguyn cht hay dung dch) cng u bt u ng
c nhit m ti p sut hi bo ho trn pha
lng bng vi p sut hi bo ho trn pha rn.
i vi cht lng nguyn cht, khi p sut ngai khng
i nhit ng c khng thay i trong sut qu
trnh ng c.
Solutions
p sut hi bo ho ca dung dch lng
p sut hi bo ho ca dd l hi cn bng vi dung
dch lng.
p sut hi bo ho ca dd bng tng p sut hi
bo ho ca tt c cc cu t c trong h. P
dd
= P
i


p sut hi bo ho ca dd lng, long cha cht tan
khng in ly, khng bay hi chnh l p sut hi bo
ho ca dung mi trong dung dch.
Solutions
P SUT HI BO HO
ca dung dch lng long phn t cha
cht tan khng in ly khng bay hi

Lng Hi
Bay hi AH
bh
> 0
Ngng t AH
nt
< 0

N
1
= N
dm
=1

N
1
= N
dm
<1 (dung dch)
P
0

P
1

K= P
1
/ N
1

K= P
0

1 0 1
N p p =
N
1
= 1 N
2
p
1
= p
0
(1 N
2
) = p
0
p
0
N
2

( )
0 0
1 0
2
p
p
p
p p
N
A
=

=
nh lut
RAOULT I
Solutions
p sut hi bo ha ca dung mi trong dung
dch lun nh hn p sut hi bo ho ca dung
mi nguyn cht cng nhit . P
1
<P
0

Phan t
dung moi
Phan tchat tan
khong bay hi
Phan t
dung moi
Phan tchat tan
khong bay hi
P
1
p sut hi bo ho ca dd lng, long cha
cht tan khng in ly , khng bay hi cng chnh
l p sut hi bo ho ca dung mi trong dung dch
Dung mi
ng cht
N
2

N
1

P
1

Solutions
nh lut Raoult II
m s s s s
C k T T T
dm ddphtu
= = A
m
C k T T T
ddphtu dm
= = A
Kh
T

ca dd
T

ca dm
T
s
ca dm
T
s
ca dd
Lng
Rn
Dung mi
nguyn cht
AT
S
AT

Solutions
Dung mi
T
si
(C) K
s
(
0
C/m) T

(
0
C) K

(
0
C/m)
Water, H
2
O
100.0 0.52 0.00 1.86
Benzen,
C
6
H
6

80.1 2.53 5.5 5.12
Ethanol,
C
2
H
6
O
78.4 1.22 -114.0 1.99
Carbon tetrachloride,
CCl
4

76.8 5.02 -22 29.8
Chloroform,
CHCl
3

61.2 3.63 -63.5 4.68
Solutions
Nhit si ca dung dch lng phn t cao
hn nhit si ca dung mi nguyn cht
) dm ( T ) ddlpt ( T
s s
>
) dm ( T ) ddlpt ( T

<
Nhit ng c ca dung dch lng phn
t thp hn nhit ng c ca dung mi
nguyn cht

Tinh th dung mi
nguyn cht

T

(H
2
O) >T

(dd)
Solutions
Nhn xt
i vi dung dch cha bo ho, nhit si l
nhit bt u si,nhit ng c l nhit
bt u ng c.Trong qu trnh si hay ng c
do nng dd tng lin tc nn nhit si tng
lin tc, nhit ng c gim lin tc.
Khi dung dch bo ho, nhit si v nhit
ng c mi l hng s.
Solutions
p sut thm thu t
S thm thu v p sut thm thu
nh lut Vant Hoff
RT C
M
= t
N
dm
=1
N
dm
<1
Mng bn thm
Solutions
Nhn xt
nh lut Raoult v Vant hoff ch ng
cho dd lng l tng v cc dd thc c
nng cht tan rt nh (dd long)
i vi dd thc (khng l tng) p sut hi ring
phn c th c gi tr ln hn (sai lch dng) hoc
b hn (sai lch m)so vi gi tr tnh theo l Raoult.
Solutions
S khc bit ca dd in ly
so vi dd lng phn t
Dung dch in ly
khng tun theo
nh lut Raoult
nh lut Vant Hoff

Dung dch in ly
dn in
Solutions
H
2
O(l) H
2
O(k)

p sut hi bo ho ca dung mi
nguyn cht ln hn p sut hi bo
ho ca dm trong dd l do cc phn t
dm t do trn b mt cht lng nhiu
hn. N
(dm ngcht)
= 1 > N
1

Solutions
H
2
O(l) H
2
O(k)

S tiu phn cht tan khng bay hi cng tng s
lm gim s phn t dung mi t do trn b mt nn
p sut hi bo ho ca dung dch cng gim nhiu.
Solutions
DUNG DCH IN LY
Dung dch in ly khng tun theo cc l Raoult v Vant Hoff
i l h s ng trng hay h s Vant Hoff
s tiu phn ch tan (s ion ,s ph t ch tan khng in ly)
s phn t cht tan ho tan
i=
m- s ion trong 1 phn t (nguyn dng >2)
Dung dich in ly 1< i s m ; Dung dch lng phn t i=1
1 mol cht (dd in ly) =N
1
+N
2
S tiu phn cht tan = i.N
2

Trong 1000g dmi s tiu phn cht tan =i.c
m
Trong 1lit dung dch s tiu phn cht tan= i.C(mol/l)
Solutions
Lng Hi
Nguyn cht N
2
=0 , N
1
=1 P
0

0
) pt ( 1 o
0
2
p
p p
p
p
N

=
A
=
Dd lng phn t, N
2
s tp cht tan =N
2

Dd in ly , N
2
i.N
2

0
) dly ( 1 0
0
2
p
p p
p
' p
iN

=
A
=
C
m
i.c
m

m s s
C ik ' T = A
m
C k . i ' T = A
C
M
(mol/l)i.c
M

RT C . i '
M
= t
Trong cng iu kin P
o
> P
1(pt)
> P
1(ly)

T
s
(dm ngcht) < T
s
(dd pt) < T
s
(dd ly)
T

(dm ngcht) >T

(dd pht) > T

(dd ly)
t (dd pht ) < t (dd ly)
Solutions
ng dng ng lut Raoult lm thay i
nhit ng c ca nc
Propylene glycol
Ethylene
glycol c
hi vi gia
sc
Dng lm ph gia
pha trong nc
(lm ngui ng c
t) nhm khc
phc nc ng
c vo ma ng.
Solutions
a) Ct, SiO
2
b) Mui m, NaCl
c) CaCl
2
chng hin tng ng bng
tuyt vo ma ng trn cc
con ng giao thng, theo bn
ta nn chn cc gii php no
sau y :
Solutions
Dung dch in ly dn in
dn in ring _ - 1cm
3
dd (s=1cm
2
;d=1cm)



| |
1 1
cm om
1

= _
_ = _ =
N
C
1000
V .
Khi pha long tng
Khi pha long v cng

= const
dn in ng lng - V cm
3
(1lgam ctan)

Khi pha long _ gim
Solutions
THUYT IN LY CA ARRHENIUS
Phn t cht in ly (ax,baz,mui)
CATION (+) v ANION(-)
HCl H
+
+ Cl
-

Gii thch c tnh dn in v do c s gia tng s
tiu phn cht tan nn dd in ly khng tun theo cc
l Raoult VantHoff
CuSO
4
(mu trng) ddCuSO
4
(mu xanh) Vsao ?
ION T DO
Solutions
Qu trnh ho tan NaCl trong nc
Cc phn t nc c cc
s ht cc ion Na
+
v Cl
-

trong mng tinh th
mui,lm yu lc ht gia
cc ion .
Khi lc ht gia cc ion
yu i, cc ion s tch ra
vb bao quanh cc lng
cc nc
Cc ion b hydrat s khuch
tn t t ra khi tinh th v
tan trong dung dch.
14.3
Solutions
THUYT IN LY CA KABLUKOB
Trong dung dch khng c ion t do
Qu trnh solvat ho
(Qu trnh hydrat ho H
2
O)

NaCl(r) + (n+m) H
2
O Na
+
.nH
2
O + Cl
-
.mH
2
O
HCl (k) + (n+m)H
2
O H
3
O
+
.(n-1)H
2
O + Cl
-
.mH
2
O
Hp cht ion qu trnh phn ly cc ion
Hp cht cng ho tr c cc qu trnh ion ho.
Cht tan
(c cc mnh)
Dung mi
(c cc)
ion solvat ho (ion hydrat ho)
Solutions
Nu cht tan c nhiu kiu lin kt ho hc khc
nhau th qu trnh phn ly theo trt t sau:

NaHSO
4
(dd) = Na+ (dd) + HSO
4
-
(dd)
HSO
4
-
(dd)+ H
2
O H
3
O
+
(dd) + SO
4
2-
(dd)

Lin kt ion

Cng ho tr phn cc mnh

S phn ly khng xy ra cho nhng lk cng ho
tr c cc yu hoc khng phn cc
Solutions
in ly o
s phn t phn ly thnh ion
Tng s phn t ho tan trong dung dch
1 m
1 i

= o
o=
0 s o s 1 o =0 dd lng phn t
o =1 in ly hon ton
Cng thc xc nh in ly

= o
( )
( ) 1 m 1
n
n n m n
i o + =
o + o
=
n- s mol cht tan ho tan
on- s mol cht tan in ly
(n - on) s mol cht
tan khng in ly
onm - s mol ion
Solutions
Cc yu t nh hng n in ly o
Bn cht cht tan v dung mi
Dung mi c cc yu o nh
Dung mi c cc mnh o ln
Nng dung dch
C gim th o tng
C 0 th o 1
Nhit tng thng o tng
Solutions
Quy c nh gi in ly
Trong dd nc 0,1N 25
0
C.
o > 30% cht in ly mnh
3%< o < 30% cht in ly trung bnh
o < 30% cht in ly yu
Solutions
CN BNG TRONG DD CHT IN LY YU
A
m
B
n
(dd) mA
n+
(dd) + nB
m-
(dd)
Qt ion ho
Qt phn t ho
Hng s in ly
| | | |
| |
n m
n
m
m
n
B A
B . A
K
+
=
Hng s in ly l hs cn bng ca qt in ly nn l lg c
trng cho mi cht in ly v dung mi, ph thuc vo nhit .
Axit hsly k hiu K
a

Baz hsly k hiu K
b

c trng cho cng
Axit - base
Trong dd nc: K
a
,K
b
< 10
-4
axit yu, base yu
Biu thc ca
l tc dng
khi lng
Solutions
QUAN H GIA K v o
AB (dd) A
+
(dd) + B
-
(dd)

Ban u C
0
in ly C
0
o C
0
o C
0
o
Cn bng C
0
(1 - o) C
0
o C
0
o
Hng s in ly:
o
o
= =
+
1
C
C
C . C
K
2
0
AB
B A
Khi o << 1 : (1 - o) ~ 1

0
C
K
~ o
Biu thc ton
hc ca l pha
long Ostwald
Solutions
AXIT - BASE YU A BC
Hng s in ly cc bc gim dn theo trt t sau:
K
1
>K
2
>K
3
>K
4

Hng s in ly chung : K=K
1
.K
2
.K
3
.K
4


Trong thc t thng ch ch n s phn ly bc th nht
Mui
a s mui thuc loi in ly mnh: KCl, NaF
Cc mui in ly km : mui axit (H+),mui baz(OH
-
),mui phc.
Solutions
HNG S IN LY CA CC AXIT A BC
Solutions
Na
2
HPO
4
(dd) = 2Na
+
(dd) + HPO
4
-
(dd)
HPO
4
-
(dd) H
+
(dd) + PO
4
-
(dd)
K
3
[Fe(CN)
6
](dd) = 3K
+
(dd) + [Fe(CN)
6
]
3-
(dd)
[Fe(CN)
6
]
3-
(dd) Fe
3+
(dd) + 6CN
-
(dd)
| || |
| |

+
=
3
6
6
3
kb
) CN ( Fe
CN Fe
K
Hng s khng bn ca phc
| |
| || |
6
3
3
6
kb
b
CN Fe
) CN ( Fe
K
1
K
+

= =
Hng s bn ca phc
Fe
3+
(dd) + 6CN
-
(dd) [Fe(CN)
6
]
3-
(dd)

Solutions
Lp lun: thc nghim cho thy trong dd khng c phn t
trung ha in Cht in ly mnh: in ly hon ton o = 1


CN BNG TRONG DD CHT IN LY MNH
Lp lun Thc t
in ly o = 1 o < 1
H s ng trng i L s nguyn Khng nguyn
dn in khi pha
long dung dch
Khng i Tng ln
Solutions
Thc t: khng tun theo L tc dng khi lng.
V d: NaCl

C
N
0.001 0.005 0.01 0.05 0.1 0.2
o 0.977 0.953 0.936 0.882 0.852 0.818
K 0.042 0.097 0.137 0.380 0.491 0.735
H s ng trng i
Hp cht
Gi tr gii
hn ca i
Nng molan
Solutions
L thuyt cht in ly mnh
Trong dung dch xut hin lc ht tng h gia cc
ion bu kh quyn ion. Khi pha long, lc ht tng
h gim, dn in tng.
Trong dd cht in ly mnh c lin hip ion, khi pha
long cc lin hip ion phn ly thnh cc ion n gin.
dng hot a thay cho nng : a = fC
in ly trn thc t : in ly biu kin.
Solutions
HOT (a) l nng hot ng mang tnh tng
qut hn hn nng v p dng l tc dng khi
lng cho mi dd cht tan cc nng khc nhau
a = fc
f- h s hot 0 < f s 1
Dd long f =1 a = c
Dd c nng cao f<1 a = c
f ph thuc vo : bn cht dung mi, nhit ,
in tch v nng cc ion.
Solutions
Phng trnh ca Debye v Huckel
I
I Az
f
i
i
+
=
1
lg
2
I
I z z A
f
m n
n m
B A
B A
+
=
+
1
lg

=
2
2
1
i i
z C I
i vi dung dch nc v 250C: A = 0,5
Khi I s 0,01 phng trnh trn c dng n gin nh sau:
I z f
i i
2
5 , 0 lg =

I z z f
m n
n m B A
B A
+
= 5 , 0 lg

Solutions
Cn bng trong dung dch cht in ly kh tan v
tch s tan.


( )
+
+
dd dd r
Cl Ag AgCl

AgCl
Cl Ag
T C C K = =
+
.

( ) ( ) ( )
+
+
m
dd
n
dd r n m
nB mA B A
n
B
m
A
B A
m n
n m
C C T
+
=
0 0 0
ln S T H T RT G
n m
B A
A A = = A
Tch s tan ca mt cht ph thuc:
Bn cht ca dung mi v cht tan
Nhit
Solutions
Tch s tan v tan ca cht in ly kh tan.
( ) ( ) ( )
+
+
m
dd
n
dd r n m
nB mA B A
S[mol/l] mS nS
( ) n m
n m
B A
n m
T
S
n m
+
=
( ) ( )
( ) n m n m
n m
n
B
m
A
B A
S n m
nS mS
C C T
m n
n m
+
=
=
=
+
tan
trong nc
Solutions
nh hng ca cc ion trong dung dch n
tan ca cht in ly kh tan.
Thm ion cng loi: S+
( ) ( ) ( )
+
+
m
dd
n
dd r n m
nB mA B A
Thm ion khc loi: S|
) n m (
B A
) n m ( n m ) n m (
B A
n m
n
B
n
B
m
A
m
A
n
B
m
A
B A
n m n m
m m n n m n
n m
f S n m f ) nS ( ) mS (
f C f C a a T
+ + +
=
= = =
+ + +
) (
) (
n m
n m
B A
n m
B A
n m
n m
f n m
T
S
+
+
=
Solutions
iu kin ho tan v kt ta ca cht ly kh tan.
Cht in ly s kt ta khi
n m
m n
B A
n
B
m
A
T C C >
+
Cht in ly s tan ht khi
n m
m n
B A
n
B
m
A
T C C <
+
Dung dch bo ha
n
B
m
A
B A
m n
n m
C C T
+
=
( ) ( ) ( )
+
+
m
dd
n
dd r n m
nB mA B A
n m
B A
T
Q
ln RT G = A
Solutions
S ion ha v tch s ion ca nc
dn in ca H
2
O = 5,54.10
-18
O
-1
.cm
-1

H
2
O + H
2
O H
3
O
+
+ OH
-

14
3 n
10 ] OH ][ O H [ K
+
= =
pH=-lg[H
+
] pOH=-lg[OH
-
]
pK=-lgK
pK
n
= pH+ POH = 14
Solutions
Ch s pH v mi trng dd
Trong nc nguyn cht v mi trng trung tnh
[H
+
] = [OH
-
] = 10
-7
pH = 7
Trong dung dch axit c mi trng axit
[H
+
] > [OH
-
] pH < 7
Trong dung dch baz c mi trng baz
[H
+
] < [OH
-
] pH > 7
Solutions

Solutions
Khi nim v axit, baz.
a. Thuyt c in ca Arrhenius
b. Thuyt proton Bronsted
c. Thuyt electron ca Lewis
Solutions
Thuyt c in ca Arrhenius
Axit: cht in ly cho ion H
3
O
+
trong nc
Baz: cht in ly cho ion OH
-
trong nc

HCl(aq) +H
2
O(l) H
3
O
+
(aq) + Cl
-
(aq)
HNO
3
(aq)+H
2
O(l) H
3
O
+
(aq) + NO
3
-
(aq)
NH
3
(aq) + H
2
O (l) NH
4
+
(aq) + OH
-
(aq)
Solutions
Thuyt proton Bronsted

Axit :cho proton HA H
+
+ A
-
Baz: nhn proton: B + H
+
BH
+
Cc cp axit baz lin hp: HA/A
-
, BH
+
/B
HA + B A
-
+ BH
+

Phn ng gia axit v baz l p trao i proton(H
+
)
gia axit ca 1cp axit- baz lin hp ny vi 1baz
ca 1 cp axit-baz lin hp khc.
Solutions
Phn ng gia cc cp axit baz lin hp
Acid + Base Base + Acid
Cp lin hp
Cp lin hp
Reaction 1 HF + H
2
O F

+ H
3
O
+


Reaction 2 HCOOH + CN

HCOO

+ HCN

Reaction 3 NH
4
+
+ CO
3
2
NH
3
+ HCO
3

Reaction 4 H
2
PO
4

+ OH

HPO
4
2
+ H
2
O

Reaction 5 H
2
SO
4
+ N
2
H
5
+
HSO
4

+ N
2
H
6
2+


Reaction 6 HPO
4
2
+ SO
3
2
PO
4
3
+ HSO
3

Solutions
D on axit, baz Bronsted
Axit l cht phi cha H
+

Phn t trung ho : HCl, HNO
3
, HF.
Cation c cha H
+
: NH
4
+

Cation kim loi trong nc : Fe
2+
(aq) ; Al
3+
(aq)..
Cation cu hnh kh tr c q
2
/ r cng ln tnh axit cng mnh
Cation c in tch v bn knh tng ng, cu hnh: 18e
(18e +2e) (18e> >8e ) tnh axit mnh hn cu hnh 8e
Anion c cha H : HSO
4
- ,
H
2
PO
4
-
.
Solutions
Al(H
2
O)
6
Al(OH)(H
2
O)
5
+ H
+

3+ 2+
Al(H
2
O)
6
+H
2
O (l) Al(OH)(H
2
O)
5
+ H
3
O
+

3+
2+
Al
3+
(aq) b thu phn
Solutions
Baz Bronsted - cht c d mt in tch m
21 , 7 ) PO H ( pK
4 3 a
2
=
Anion: Cl
-
, NO
3
-
, SO
4
2-
, PO
4
3-
.
Phn t cng ho tr phn cc : NH
3
..
Cht lng tnh- cht va c kh nng cho H
+
va
c kh nng nhn H
+.
Cc hp cht c cha H thng l cht lng tnh
HCl + H
2
PO
4
-
Cl
-
+ H
3
PO
4

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

33 , 10 ) CO H ( pK
3 2 a
2
=
Solutions
Dung mi proton ho
L hp cht cng ho tr phn cc c cha H nn c
kh nng trao i proton (cht lng tnh)
Thng to lk H
2
nn T
s
v T
nc
cao.
C tnh phn cc mnh nn c kh nng ho tan
nhiu cht (c cc).
C th t ion ho mt phn khi trng thi lng.
Hng s cn bng gi l hng s t proton ho K
d


Solutions
H
2
O + H
2
O H
3
O + OH
-
k
n
= [OH
-
][H
3
O
+
]

NH
3
+ NH
3
NH
2
-
+ NH
4
+
k
d
= [NH
2
-
][NH
4
+
]
HD + HD D
-
+ H
2
D
+
K
d
= [D
-
][H
2
D
+
]
Solutions
S in ly ca axit v baz l kt qu ca p trao
i proton gia axit v baz vi dung mi.
NH
3
(aq) + H
2
O (l) NH
4
+
(aq) + OH
-
(aq)
axit baz axit baz
Solutions
S in ly ca axit v baz trong nc
Axit: HA + H
2
O A
-
+ H
3
O
+
| || |
| | HA
A O H
K
3
a
+
=
Baz: B + H
2
O BH
+
+ OH
-
| || |
| | B
OH BH
K
b
+
=
K
a
cng ln th tnh
axit cng mnh
K
b
cng ln th tnh
baz cng mnh
Solutions
i vi cp axit baz lin hp:
HA + H
2
O A
-
+ H
3
O
+
] [
] ][ [
3
) (
HA
A O H
K
HA a
+
=
A
-
+ H
2
O HA + OH
-
] [
] ][ [
) (

A
OH HA
K
A b
n
A b
HA a
K OH O H
A
OH HA
x
HA
A O H
K K = = =
+

] ][ [
] [
] ][ [
] [
] ][ [
3
3
) (
) (
pK
a
+ pK
b
= pK
n
= 14

K
a
.K
b
= K
d

pK
a
+ pK
b
= pK
d

Axit cng mnh (K
a
) th baz lin hp l baz yu(K
b
)
Axit cng yu (K
a
) th baz lin hp l baz mnh (K
b
)

K
a
.K
b
= K
n

Solutions
HNG S IN LY CA CC BASE YU
Solutions
HNG S IN LY CA CC AXIT YU V BASE LIN HP

25
0
C
Solutions
Hiu ng san bng dung mi
HA + H
2
O A
-
+ H
3
O
+
H
3
O
+

l ax mnh nht trong dd
HA + H
2
O A- + H
3
O+ H
3
O+ l ax mnh nht trong dd
Trong dung mi H
2
O : H
3
O
+
l axit mnh nht,
OH
-
l baz mnh hnt
Trong dung mi NH
3
: NH
4
+
l axit mnh nht
NH
2
-
l baz mnh nht
Trong dung mi HD : H
2
D
+
l axit mnh nht
D
-
l baz mnh nht
Solutions
nh hng ca dung mi n
cng axit baz
Hng s t proton ho (K
d
)
HD + HD D
-
+ H
2
D
+
K
d
= [D
-
][H
2
D
+
]
K
d
cng ln th tnh axit ca dung mi cng mnh.
i lc proton (AP) HD + H
+
=H
2
D
+
AH = -AP
AP cng ln th dung mi c tnh baz cng mnh
Solutions

Dung mi c AP th tnh axit ca cht tan tng
tnh baz ca cht tan gim

Trong nc, CH
3
COOH l axit yu
Trong NH
3
, CH
3
COOH l axit mnh
Dung mi c AP th tnh axit ca cht tan gim
tnh baz ca cht tan tng
Trong dung mi HF,HClO
4
khng cht no th hin tnh axit
HNO
3
+ HF (dm) H
2
NO
3
+
+ F
-

NH
4
OH l baz yu trong dung mi nc
NH
4
OH l baz mnh trong dung mi axit acetic
Solutions
Thuyt electron ca Lewis
Axit Lewis: l tiu phn c d mt in tch dng v
orbital ho tr trng nhn cp electron lin kt t baz.


D on axit Lewis:
Hu ht cc cation kim loi (Ag
+
, Co
3+
, Cr
3+
, Mg
2+..)
Cc halogenua ca B, Al, Si, Sn
Cc hydrua ca B,Al
Cc hp cht c lk i trong nhng k thch hp cng
th hin tnh axit
Thuyt Lewis dng gii thch qu trnh to phc v tnh bn
ca phc.
Solutions
D on baz Lewis:
Cc anion : Cl
-
, Br
-
, OH
-
Phn t trung ho hay ion c cha nguyn t (N,O )
cn cp e ho tr t do nh : NH
3
, amin , ru, xeton..
Base Lewis: cht cho cp electron.
N H

H
H
acid
base
F B
F
F
+
F B
F
F
N H
H
H
Ag
+
+ 2NH
3
[Ag(NH
3
)
2
]+


Solutions
H
+

H O H


+ OH
-

acid base
N H

H
H
H
+

+
acid base
N H
H
H
H
+
base
acid


Solutions
HCl, axit mnh HF, axit yu
[H
+
] = [HCl]
[H
+
] < [HF]
Solutions
pH ca dd long axit v baz mnh
Axit mnh HA H
+
+ A
-
C
a
C
a

a
H
C lg C lg pH = =
+
Baz mnh MOH M
+
+ OH
-
C
b
C
b

b
b
OH
C pOH pH
C C pOH
lg 14 14
lg lg
+ = =
= =

C
a
>10
-7
ion.g/lit
C
b
>10
-7
ion.g/lit
Solutions
Axit mnh v base mnh
HCl CH
3
CO
2
H
Thymol Blue ch th
pH < 1.2 < pH < 2.8 < pH
Solutions
pH ca dd axit yu v base yu.
Axit yu HA + H
2
O H
3
O
+
+ A
-
Cn bng C
a
(1- o) C
a
o C
a
o
a a
a
a
a a
O H
C K
C
K
C C C
3
= = o =
+
( ) ( )
a a a a
O H
C lg pK
2
1
C lg K lg
2
1
C lg pH
3
= = =
+
( )
b b
C pK pOH lg
2
1
= ( )
b b
C pK pH lg
2
1
14 =
o<<1, K
a
C
a
>> K
n

Baz yu MOH M
+
+ OH
-

Cn bng C
b
(1- o) C
b
o C
b
o

o<<1, K
b
C
b
>> K
n

Solutions
i vi axit , base yu a bc
Khi tnh pH dung dch ta ch da vo bc phn ly
th nht
7
a
10 . 3 , 4 K
1

= V d : tnh pH dung dch H

2
CO
3
0,01M .
| | ( ) | | 19 , 4 10 lg 10 . 3 , 4 lg
2
1
C lg pK
2
1
pH
2 7
a a
1
= = =

Solutions
Hng s in ly ca cc axit v base yu
25
0
C
Solutions
o pH ca gim
o pH ca dd NH
3

Solutions
Cc phng php o pH cho cc dd nc
(a) Giy o pH (nh tnh) (b) My o pH(nh lng)
Solutions
pH ca dung dch m.
nh nghi: Dung dch m l dd c pH const khi thm
lng nh axit mnh hoc baz mnh hoc pha long dd.
Cu to (HA / A
-
)
m axit: axit yu + mui ca n CH
3
COOH+CH
3
COONa
m baz: base yu + mui ca n NH
3
.H
2
O+ NH
4
Cl
m trung tnh : hn hp cc mui axit yu
C ch tc dng ca dung dch m
CH
3
COOH CH
3
COO
-
+ H
+
(1)
CH
3
COONa CH
3
COO
-
+ Na
+
Thm axit mnh: cb (1)
Thm base mnh: H
+
+ OH
-
H
2
O: lng H
+
cb (1)
Pha long dd, in ly CH
3
COOH
Solutions
CH
3
COONa CH
3
COO- + Na
+
Cm Cm
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+

C
a
(1-o) (C
a
o + C
m
C
m
) C
a
o

pH ca dung dch m axit ( HA + MA)
a
m
a
m
a
a 3
C
C
lg pK
C
C
lg K lg ] O H lg[ pH + = = =
+
| || |
| |
| |
a
m 3
3
3 3
a
C
C O H
COOH CH
COO CH O H
K
+ +
= =
m
a
a 3
C
C
K ] O H [ =
+
PH ca dd m base ( MOH + MA )
|
|
.
|

\
|
+ =
b
m
b
C
C
lg pK 14 pH
Solutions

HA (dd) + MOH(dd)
AH
thu phn
>0
S phn t mui ho tan
s phn t mui thu phn
Phn ng thy phn l phn ng l phn ng nghch ca p
trung ho.
MA (dd) + H
2
O
pH ca dung dch mui
Phn ng thu phn l p trao i ion gia mui v nc, c kh
nng lm thay i pH mi trng.
AH
trung ho
<0
Hng s cn bng ca qu trnh thu phn K
t

thu phn h =
s 1

Solutions
Do mui c lk ion nn khi ho tan trong nc s phn
ly han ton thnh cc ion b hydrat ho
M
+
(aq) + A
-
(aq) +H
2
O MOH (aq) + HA (aq) ; AH >0
M
+
.nH
2
O / M(OH).(n-1)(H
2
O) l cp axit- base lin hp
HA / A
-
l cp axit - baz lin hp
Theo thuyt axit - base Bronsted :
Cation ca mui (M+) l axit bronsted
Anion ca mui ( A
-
) l base bronsted
Vy p thu phn thc cht l p trao i proton
gia cc ion ca mui vi cc pt nc.
Hay p thu phn l p axit base Bronsted.
Solutions
Mui no s b thu phn ?
Nu cation ca mui (M+) l axit mnh hn nc
(MOH l base yu), n s nhng H
+
cho nc
cation mui b thu phn lm cho pH
mtr
<7
Ag
+
nH
2
O + H
2
O Ag(OH)(n-1)H
2
O + H
3
O
+

NH
4
+
(aq) + H
2
O NH
3
(aq) + H
3
O
+

Nu anion ca mui (A
-
) l baz mnh hn nc
(HA l axit yu), n s nhn H
+
ca nc lm tng OH
-

anion mui b thu phn lm cho pH
mtr
>7

CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-

Tt c cc mui (MA) u b thu phn tr mui c
to thnh t axit mnh (HA) v base mnh (MOH)
Solutions
Cation cu hnh kh tr c q
2
/ r cng ln tnh axit cng
mnh nn thu phn cng mnh.
V d : K
a
[Mg
2+
(aq)] > K
a
[Ba
2+
(aq)] Mg
2+
(aq) thu phn
mnh hn Ba
2+
(aq).
Cation c in tch v bn knh tng ng, cu hnh: 18e
(18e +2e) (18e> >8e ) tnh axit mnh hn cu hnh 8e
nn thu phn s mnh hn
V d : Mg
2+
(aq) thu phn yu hn Hg
2+
(aq)
Solutions
Hng s K
a
ca cc ion kim loi trong nc 25
0
C

Ion kim loi K
a
Fe
3+
(aq) 6 x 10
-3

Sn
2+
(aq) 4 x 10
-4

Cr
3+
(aq) 1 x 10
-4

Al
3+
(aq) 1 x 10
-5

Be
2+
(aq) 4 x 10
-6

Cu
2+
(aq) 3 x 10
-8

Pb
2+
(aq) 3 x 10
-8

Zn
2+
(aq) 1 x 10
-9

Co
2+
(aq) 2 x 10
-10

Ni
2+
(aq) 1 x 10
-10
Tnh axit tng dn
Thu phn mnh dn
Solutions
CNG CA CP AXIT BASE LIN HP
Cc anion (A
-
) c tnh base cng mnh s thu phn
cng mnh trong nuc.
HA A
-

Solutions

pH ca dung dch mui

Mui to thnh t axit mnh v base yu (M
+
+H
2
O pH < 7)



HA MOH
Mui to thnh t axit mnh v base mnh
MA khng b thu phn pH 7

Mui to thnh t axit yu v base yu ( M
+
+A
-
+ H
2
O )

Mui to thnh t axit yu v base mnh (A
-
+H
2
O pH >7)

Solutions
Mui khng tp Cation tp
(Axit)
Anion tp
(Base)
pH
CH
3
COONH
4
NH
4
+
CH
3
COO
-

7
AlCl
3

Al
3+

<7
FeCl
2

Fe
2+

<7
KClO
4
Khng 7
Na
2
S S
2-
>7
NaF F
-
>7
NaBr Khng 7
NH
4
CN
NH
4
+

CN
-
>7
NH
4
F
NH
4
+

F
-
<7
pK(NH
3
)=4,76; pK(CH
3
COOH)=4,75;pK(HCN)=9,2;pK(HF)=3,18
K<K
K>K

KK

Solutions
Solutions
Mui to thnh t axit yu (K
a
) v baz mnh PH >7
S in ly: MA M
+
(ax
y
) + A
-
(base mnh hn H
2
O)

S thy phn: A
-
+ H
2
O HA + OH
-
C
m
(1-h) C
m
h C
m
h
Hng s thy phn:

thy phn:



Tnh pH:

| || |
| |
| |
| || |
| || |
a
n
t
K
K
OH H
A H
HA
A
OH HA
K = = =
+
+

| || |
| |
( )
( )
2
m
2
m
m
2
m
t
h C
h 1
h C
h 1 C
h C
A
OH HA
K ~

= =

m a
n
m
t
C K
K
C
K
h = =
| |
a
m n
m a
n
m m
K
C K
C K
K
C h C OH = = =

| |
| |
m
a n n
C
K K
OH
K
H = =

+
( ) ( )
m a m a n
C lg pK
2
1
7 C lg pK pK
2
1
pH + + = + + =
>7
Solutions
Mui to thnh t axit mnh v baz yu (K
b
) pH<7
S in ly: MA M
+
(axit mnh hn nc) + A
-
(base
y
)

S thy phn: M
+
+ H
2
O MOH + H
+
C
m
(1-h) C
m
h C
m
h
Hng s thy phn:

thy phn:


Tnh pH:


| || |
| |
| |
| || |
| || |
b
n
t
K
K
OH H
OH M
MOH
M
H MOH
K = = =
+
+ +
+
| || |
| |
( )
( )
2
m
2
m
m
2
m
t
h C
h 1
h C
h 1 C
h C
M
H MOH
K ~

= =
+
+
m b
n
m
t
C K
K
C
K
h = =
| |
b
m n
m b
n
m m
K
C K
C K
K
C h C H = = =
+
( ) ( )
m b m b n
C lg pK
2
1
7 C lg pK pK
2
1
pH + = =
<7
Solutions
Mui to thnh t axit yu (K
a
) v base yu (K
b
)
S in ly: MA M
+
(axit mnh hn nc) + A
-
(base mnh hn nc)

S thy phn: M
+
+ A
-
+ H
2
O HA + MOH

C
m
(1-h) C
m
(1-h) C
m
h C
m
h
Hng s thy phn:


thy phn:


Tnh pH:


| || |
| || |
| |
| || |
| |
| || |
| || |
b a
n
t
K K
K
OH H
OH M
MOH
A H
HA
A M
MOH HA
K = = =
+
+ + +
| || |
| || |
( )
( ) ( )
2
2
2
2
2
m
2
m
t
h
h 1
h
h 1 C
h C
A M
MOH HA
K ~

= =
+
b a
n
t
K K
K
K h = =
| |
| |
| |
b
a n
b a
n
a a a
m
m
a a
K
K K
K K
K
K h K
h 1
h
K
) h 1 ( C
h C
K
A
HA
K H = = ~

= =

+
( ) ( )
b a b a n
pK pK
2
1
7 pK pK pK
2
1
pH + = + =
Solutions
NHN XT
Hng s thu phn K
t
ph thuc vo :
Bn cht ca mui v nhit
thu phn h ph thuc vo:
K
a
v K
b
ca axit v baz lin hp vi cc ion ca
mui, c to thnh trong qt thu phn,chng c gi
tr cng nh th thu phn cng tng.
C
m
cng nh th thu phn tng (tr mui to
thnh t axit yu v baz yu )
Nhit tng th thu phn tng.
Solutions
Cch tnh pH ca cc dung dch.
a. pH ca dd axit mnh v base mnh.
b. pH ca dd axit yu v base yu.
c. pH ca dung dch m.
d. pH ca dung dch mui
a
C lg pH =
b
C pH lg 14 + =
( )
a a
C pK pH lg
2
1
=
( )
b b
C pK pH lg
2
1
14 =
a
m
a
C
C
lg pK pH + =
|
|
.
|

\
|
+ =
b
m
b
C
C
lg pK 14 pH
( )
m b
C pK pH lg
2
1
7 + =
( )
m a
C pK pH lg
2
1
7 + + =
( )
b a
pK pK pH + =
2
1
7
Solutions
Pha long dung dch
Pha long nng
dung dch A t 1M
xung 0,02M
pipet
Bnh
nh
mc
ddA
1M
Dng pipet ht 10,00 ml dd A 1M
cho vo bnh nh mc 500ml
+nc vo cho n vch chun
ca bnh lc u ddA 0,02M
Solutions
Phn ng trung ho
HCl (dd) +NaOH(dd) = NaCl (dd) + H
2
O

H
3
O
+
+ OH
-
= 2H
2
O ; AH
0
298
= -13,36 kcal = - 55,84 kJ
Hiu ng nhit tiu chun l hng s, khng ph thuc vo loi
axit mnh v base mnh tham gia phn ng.
Phn ng n cng, khng c phn ng thu phn xy ra
im tng ng : V
NaOH
.C
NaOH
(N) = V
HCl
.C
HCl
(N)
Ti im tng ng pH =7
Solutions
Dng php chun axit base
xc nh nng axit


Cho dd NaOH 0,10N
vo buret ti vch
chun (mc 0)
Cho 10,00 ml dd axit HCl cha bit
nng + 100ml nc ct + 3 git
phenolphatalein vo bnh tam
gic (erlen)
V
NaOH
.C
NaOH
(N) = V
HCl
.C
HCl
(N)
0
Solutions
Chun dd HCl bng dd NaOH
Nh t t dd NaOH t burt xung bnh tam gic v lc
u dd trong bnh cho n khi dung dch trong bnh bt
u chuyn sang mu hng nht (bn trong 30 giy)
c th tch ddNaOH dng trn buret V=24,6 ml
tnh nng dd HCl theo l ng lng. C
HCl
= 0,25N
ddNaOH
0,10N
Dd HCl
C
HCl
?
0
24,6