Chng III

CAN BANG HOA

HOC
I.

nh luat tac dung khoi lng va

hang so can bang

II. Can bang hoa hoc trong he d the

III. Cac yeu to anh hng en can
bang hoa hoc
IV. nh ly nhiet Nernst
V.

Cac phng phap xac nh hang

I. NH LUAT TAC DUNG KHOI

LNG VA HANG SO CAN BANG
1. NOI DUNG NH LUAT
Xet phan ng ong the:

bB dD

k1
k2

gG rR

v1 k1C
Toc o p/ thuan:

b
B

Toc o p/ nghch:
v2 k2 C

g
G

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607010 - Chng 3

d
D

r
R


bB dD

k1
k2

gG rR

Ban au v1 > v2, sau o v1 giam

dan, v2 tang len.
Khi v1 = v2 th phan ng at can
g r

k
C
C
1
G
R
b d Luc go,
r
bang.
ta
c:
K

C
kC C k C C
1

b d
B D
CAN

k
C
C
2

Kc c goi la HANG SO
B

BANG cua p.
Gia tr cua hang so can bang
ac trng cho can bang cua phan
ng ieu kien xac nh, no
khong
thay oi
khi thay oi nong 3
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cb

Hnh 3.1. Can bang hoa hoc at

c t hai pha thuan va nghch
cua phan ng H2 + I2 = 2HI
HI, %
100

2HI =H2+I2

80
60

H2+I 2 =2HI

40
20
0
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25

50

75

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100

t (phu
t)
4

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NH LUAT TAC DUNG KHOI

LNG
(do Guldbrg va Waage a ra nam
1867)
Khi mot he ong the at en
trang thai can bang, th tch nong
o cua cac san pham phan ng
chia cho tch nong o cua cac chat
phan ng luon luon la mot hang
so
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2. QUAN HE GIA G VA HSCB

AD cac phng trnh :

G g G r R b B d D

i RT ln Pi
o
i

G g r b d
o
G

o
R

o
B

o
D

RT ( g ln PG r ln PR b ln PB d ln PD )

G G RT ln P
o

(1)

Trong o:G o g Go r Ro b Bo d Do
va
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g r
G R
b d
B D

P P
P
P P

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10

Khi phan ng at can bang th G

= 0, ta
o co:
(2)
G RT ln RT ln K

P cb

G RT ln K P RT ln P RT ln P
KP
(3)
(1) (3) la cac phng trnh ang
nhiet Vant Hoff, la nhng phng
trnh c ban cua ly thuyet ve
CBHH
ap dung cac ket qua cua
nhiet ong hoc (tnh toan da
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12

3. CAC DANG KHAC NHAU CUA

HSCB
Cac
chat co the bieu dien bi cac nong o khac
nhau nen cung co cac dang HSCB khac nhau.

PGg .PRr
CGg .C
Rr
g r b d
n
K p b d
K c RT
RT
b
d
PB .PD cb CB .C D cb
X Gg . X Rr
g r b d
n

KX P
P
b
d
X B . X D cb

n .n

n .n cb
g
G
b
B

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r
R
d
D

g r b d

n
i cb

K n

607010 - Chng 3

n
i

RT
Kn

V cb
cb
13

Cac dang khac nhau cua HSCB:

K p K c RT K X P K n
n

khi n 0

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ni

RT
Kn
V

K p K x K X Kn
th

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14

4. XET CHIEU
TRONG PHAN
NG HOA HOC
P
G RT ln K P RT ln P RT ln
(4)
KP
T cac pt (1), (3), (4), ta co the xet
chieu cua phan ng hoa hoc tng t
nh khi xet G:

Neu Kp > p

phan ng t xay ra theo chieu thuan

Neu Kp = p
phan ng at can
bangKp < p phan ng theo chieu
Neu
nghch
Tnh toan p giong nh Kp, nhng
khac :
- Kp ng vi trang thai can bang

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15

II. CAN BANG HOA HOC TRONG

HE D THE
1.Ap dung phng trnh Vant Hoff trong
DUNG DCH
Co the bieu dien HSCB theo cac loai
nong o khac nhau, tr trng hp
o*
bieu
dien
theo
ap
suat.
i i RT ln X i
Hoa the cua cau
t i:
GT = GT0* + RT ln
Suy ra cac

X 0* = - RTln K
he thc:
G
T

Quan he cua
cac HSCB:
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Kn Kc V
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K X ni

16

2. CAC PHAN NG TRONG HE D

THE:
Thng gap phan ng trong he
d the, ma trong o cac chat ton
tai trong
khac =
nhau,
v du:
Fe O cac
(r) +pha
3 CO(k)
2 Fe(r)
+ 3
2

COBr
(k)(l) +
2 2

H2 (k)

2 HBr(k)

Neu cac chat ran va long trong

phan ng khong tao dung dch, HSCB
ch phu thuoc vao thanh phan kh:
CaCO3 (r ) = CaO (r ) +
CO2 (kx) .P

Kp

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CaO

CO2

xCaCO3

K p' PCO2

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CaCO3 (r ) = CaO (r ) + CO2 (k )

`

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18

3. Ap suat phan
ly:
nhiet o xac nh, KP luon la hang so,

K P PCO2

CB

= const

P goi la ap suat phan ly

tr

CO2

Gia
tr
thoa

CB

nhiet o P
PCO2
quyen)
CO(kh
2
CB
=
goi la nhiet o phan ly

Gia tr nhiet o
thoa
=
1
PCO2
CB
atm
goi la nhiet o phan
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V du: Ap suat phan ly cua CaCO3

phu thuoc vao nhiet o theo phng
trnh:
lg PCO2

= - 8695/T + 7,54

(CaCO3 )

cho PCO2
4
atm

(CaCO3 )

= PCO2

(kh quyen)

= 3,0.10
tm c

Tphanly = 512oC
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20

V du: CaCO3 (r ) = CaO (r ) + CO2

(k )
Xet ieu kien ang nhiet:
(PCO2/CaCO3)cb > PCO2/KK : p xay ra theo chieu
chuan
(PCO2/CaCO3)cb < PCO2/KK : p xay ra theo
chieu nghch,
la chieu
taobang,
thanhay
(PCO2/CaCO3)cbtc
= PCO2/KK
: p can
CaCO
3 CaCO
la gii
han 3 ben
cua s phan ly va ben
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21

Xet ieu kien

a nhiet:
(PCO2/CaCO3)cb = Pkh quyen = 1atm:

T
tang

s phan ly xay ra manh liet

T (PCO2/CaCO3)cb en khi
(PCO2/CaCO3)cb=PCO2/KK
s phan ly bat au xay ra
nhiet o thng, (PCO2/CaCO3)cb <
PCO2/KK :
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CaCO3 ben, khong phan ly

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23

III. CAC YEU TO ANH HNG EN

CAN BANG HOA HOC
Co 2 loai yeu to anh hng en
can bang hoa hoc:
* Lam thay oi HSCB

Lam thay oi thanh phan cua

hon hp can bang
NHIET O
* Khong lam thay oi HSCB

Lam thay oi thanh phan cua

hon hp can bang
AP SUAT, THANH
HON HP
607010 - Chng PHAN
3
24

10/24/16

Nguyen
ly
Le
Chaterlier
Khi
tac dung t ngoai vao he can
bang bang cach thay oi mot ieu
kien nao o co anh hng en
can bang, th v tr can bang cua
he se dch chuyen ve pha lam
- Neu tang nhiet o, can bang se
giam hieu qua tac dung o.
dch chuyen theo chieu THU NHIET
- Neu giam nhiet o, can bang se
dch chuyen theo chieu TOA NHIET
Giai thch:
- Qua trnh thu nhiet se lam giam
s
tang
nhiet
- Qua
trnh
toao
nhiet se lam giam
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25

1. Anh hng cua nhiet o en

HSCB:
a/ Phng trnh ang ap Vant Hof

G RT ln K P
o
T

Xuat phat t hai phng trnh:

G
H

2
T T
T

Suy ra:

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o
ln K p
H

2
T P RT
o
lgK p
H (cal )

2
T P 4,575T
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26

b/ Phng trnh dang tch phan

Xuat phat t 2 phng trnh:

Suy ra:

d lnKp = dT
ai
+ I
HT = Ho +

i 1

1 Ho
1
1
1
2
2
lnK P
ao lnT aT
a2T a2T I
1
R
T
2
6
2

J
I = phan
trong o I la hang so tch
R
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27

Tng t co the tch phan xac

nh vi can t T1 en T2 tng
ng KP,T1 en KP,T2:

1 1
T2 1
Ho
ao ln a1 T2 T1

K P ,T2 1
T2 T1
T1 2

ln

K P ,T1 R 1

1
2
2
2
2
a2 T2 T1 a2 T2 T1

2
6

Khi HT = const (khong phu thuoc

vao nhiet o), tch phan thu c:

H
lnK P I
RT

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ln

K P ,T2
K P ,T1

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H 1 1

R T2 T1
28

c/ Tnh theo the ang ap rut gon

T cac cong thc trong chng 2:
o
o

H
o
o
T
o
GT Ho T .

o
o

H
o
o
T
298
GT H298 T .

Suy ra:
o
o
o
o
o

H o
H o
GT
T
T
*
R ln K P

T
T
T
T
T
T*
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GTo HTo
T

la
the
gon T K
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rut
29

d/ Ap dung nguyen ly Le Chaterlier

Ve o th
H
lnK P I
t phng trnh:
RT
lnK

lnK

>90

(a) H > 0
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<90o

1/T
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(b) H < 0

1/T
30

Suy ra:
- Neu H > 0 (phan ng thu nhiet):
KHI T TANG, TH
KP TANG
CB dch chuyen theo chieu thuan
= thu nhiet
- Neu H < 0 (phan ng toa nhiet):
KHI T TANG, TH
KP GIAM
CB dch chuyen theo chieu nghch =
thu nhiet
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V du:

N2

+ O2 = 2 NO + 43,2 cal

(1)
2NO + O2 = 2 NO2 - 26,7 cal
(2) - Qua trnh thu nhiet
Xet (1):
- nhiet o cao, CB dch
chuyen theo chieu tao NO
(chieu thu nhiet) la chieu
lam giam s tang nhiet o
Xet (2): - Qua trnh toa nhiet
- nhiet o cao, CB dch
chuyen theo chieu tao NO va
O2 (chieu thu nhiet) la chieu
lam giam
s tang nhiet o
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32

2. Anh hng cua ap suat tong

cong en HSCB:
He ngng tu
ap
suat
khong
anh
(ran va long)
hng en HSCB
He kh:

Kp = KX Pn =
const

* n > 0: khi ap suat tang, Pn tang

do o KX phai giam - tc la CB
theo
chieu
nghch.
* chuyen
n < 0: dch
khi ap
suat
tang,
Pn giam
do o KX phai tang - tc la CB
dch
theo
thuan.
* chuyen
n = 0: khi
o
K chieu
= K = const
X

ap suat khong anh hng en CB .

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Lu y: KP ch phu thuoc vao

nhiet o
KX phu thuoc vao nhiet o
Khi
va
ap
suat
ap
suat
tang:
CB dch chuyen theo chieu lam
giam ap suat
= chieu lam giam
V du: N2 + so
3H2mol
= 2 NH3
n = 2 4 = 2 < 0 : he giam ap
Khi ap suat tang, trong he xay ra theo
hng lam giam ap: hng tao ra NH3
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34

3. Anh hng cua cac chat khong

tham gia phan ng (chat tr):
TRONG DUNG DCH: Kc = Kn(V) -n =
Khi
chat tr hay dung moi tang lam
const

cho V tang, e gi Kc= const bat

buoc Kn phai thay oi

n
CBTRONG
b chuyen
dch
ve
pha
lam
tang
HE KH
:K
=
K
(P
/

n
)
=
p
n
i
so
mol
len.tham gia phan ng tang
Kh
khong
const
tc la ni tang

Lu

(giai
thch
anh
hng
tng
y: Kc ch phu thuoc vao T
t phan III.3.2 ).
Kn phu thuoc vao T va P va
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4. Anh hng cua thanh phan hon

hp au:
Hieu suat h% cua phan ng la t
le cua phan san pham trong hon hp
can bang.
o chuyen hoa i cua chat i tham
gia phan ng bieu dien t so cua
phan a phan ng cua chat o.
Nhan xet:
h (%) at cc ai khi
t le thanh phan hon hp p = t le
he so t lng trong phng trnh phh.
i tang len khi
tang thanh phan chat j tham gia
vao phan
ng
(j i)
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3
36

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37

IV. NH LY NHIET NERNST

1. nh ly nhiet Nernst
Trong he ngng tu chat nguyen chat
tinh the hoan chnh, ng H = f(T)
va G = (T) khong nhng ch gap
nhau ma co tiep tuyen chung 0 K
H, G

Con c
goi la:
nh ly
tiep
tuyen
10/24/16

H=f(T)

G= (T)
T

S phu thuoc nhiet o

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38

Bieu thc toan hoc bieu dien nh

ly nhiet Nernst:
H
G
lim
lim

T 0
T

0
T
T

limH limG
T 0

T 0

He qua:
1) Tiep tuyen chung cua hai ng
cong H= f(T) va G= (T) tai 0 K th
song song vi truc nhiet o
H
G

Ngha la:lim
lim
0

T 0
T 0
T
T

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39

He qua:
2) Xuat phat t:
G
G
S 0 limS 0

S lim
T 0
T 0
T P
T P
H
H

lim

C
P

T 0
T P

limCP limCV 0
T 0

T 0

nh e Planck: Entropy cua cac

chat ran nguyen chat, co cau
tao tinh the hoan chnh, 0K th
bang
khong.
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- Chng 3
40

2. Ap dung nh ly nhiet Nernst

Ap dung nh ly Nernst e tnh c
entropy tuyet oi, tnh c cac hang
so I, J va t o tnh c G va KP
theo ly thuyet.
1) He ngng tu gan 0 K
Ta co:CP 0 H

const

1
1
2
3
ma : HT Ho aoT aT
a3T ...
1
2
3
HT
1
1
ao aT
a3T ... 0
1
T
2
3

Suy ra: ao = 0
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41

 G
T (2.51): G = H +
JT

J 0
P

Suy ra: J = 0 va I =- J/R = 0

Vay cac hang so tch phan khong
xac nh trong s dung nh ly nhiet
Nernst oi vi he ngng tu (long va
ran) co gia tr bang khong: ao = 0;
Do o hang so
can
co dang:
J = 0;
I = bang
0
1 Ho 1
1
1
2
2
ln K P
aT
a2T a2T
1
R
T
2
6
2

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42

2) He kh
Trong he kh Nernst thu c phng
trnh co dang sau: H K

ln K P

Trong o:

RT

dT j

j la hang so hoa hoc thc:

j = jcuoi - jau

Gia tr cua j c cho trong so tay cac ai

lng nhiet ong.
Cac ai lng khac trong phng trnh ch
tnh cho pha kh (neu phan ng d the ).

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43

Phng trnh rut gon cua Nernst

(tnh gan ung
H):
298

ln K P

4,575T

Trong o:
n = nkh
au

1,75n.lgT i

cuoi

-n

kh

i = ikh cuoi - ikh

i c goi la hang so hoa hoc

qui c, c cho trong bang tra
so lieu nhiet ong

au

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44

V. CAC PHNG PHAP XAC NH

HSCB
(T OC)
* Phng phap trc tiep: xac nh
nong o hay ap suat trang thai
can bang
* Phng phap gian tiep: phan tch
cac ai lng hoa ly (P, V, d, cng
o mau, o dan ien, chiet suat
) co quan he nong o hay ap
*
Phng phap nhiet ong: tnh toan
suat
cac ai lng nhiet ong (nh G)
e suy ra HSCB
* Phng phap ien hoa: xac nh
sc ien ong E cua pin ien hoa
e
tnh HSCB
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45

VI. CAN BANG HOA HOC TRONG HE

THC
1. Fugat (hoat ap) va he so fugat

G P G o RT ln P
i io RT ln Pi
GT GTo RT ln P

He ly tng: PV

RT

He thc:

a
P 2 V b RT
V

Dung khai niem

FUGAT e dang
cua cac phng
trnh nhiet ong
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RAT PHC
TAP
P
o

607010 - Chng 3

G G RT ln f
i io RT ln fi
o
GT GT RT ln f
46

Fugat f la mot ham so cua ap

suat ma khi thay no vao v tr cua
ap suat trong cac phng trnh
nhiet ong th nhng phng trnh
f
nay van gi
nguyen dang n

He so fugat:
gian nh oi Pvi kh ly tng f =
( P ).
f
1 lim lim 1
Kh
ly

T 0 P
T 0

1
tng:
Kh thc:
Hang so can K
bang:
f K .K P
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2. Dung dch thc va hoat o

Hoat o a la mot ham so cua
nong o (tng ng) ma khi thay no
vao v tr cua nong o trong phng
trnh nhiet ong th nhng phng trnh
nay van gi nguyen dang
n gian
o
i tng.
i RT ln ai
nh oi
vitrnh
dung dch ly
Cac
phng
nhiet ong khi s
o

G
dung hoat o
T
T RT ln a

a
He so hoat o:

Hang so canKbang:
a K .K P
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BAI TAP

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