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HA L 1
NGUYN HU SN
MN HC
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NI DUNG 30 tit
Chng 1. Nhit ha hc
Chng 2. Chiu v gii hn ca qu trnh
Chng 3. Cn bng ha hc
Chng 4. L thuyt cn bng pha
Chng 5. Cn bng pha trong h mt cu t
Chng 6. Dung dch, cn bng lng - hi
Chng 7. Cn bng lng rn
Chng 8. Ha keo
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CHEMICAL THERMODYNAMICS
CHNG 1
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MUC TIEU CUA NHIET ONG HOC
Nghien cu cac quy luat ve s bien chuyen tng ho cua
hoa nang va cac dang nang lng khac trong cac qua trnh
hoa hoc.

Nghien cu cac ieu kien t dien bien (phan ng hoa
hoc) va cac ieu kien ben vng (trang thai can bang) cua
cac he hoa hoc.
5
MOT SO KHAI NIEM C BAN
Systems and Surroundings (H
thng v mi trng)

System (H thng): part of the
universe we are interested in.

Surroundings(mi trng ): the rest
of the universe.
6
MOT SO KHAI NIEM C BAN
He hoa hoc la lng nhat nh cua mot hay nhieu chat
ieu kien nhiet o, ap suat va nong o nhat nh(trong
nghin cu nhit ng hc goi la he thng - system)
H m l h trao i c vt cht v nng lng vi
mi trng
H kn l h ch trao i nng lng vi mi trng
He co lap la he khong co s trao oi nng lng va vt
chat vi moi trng ben ngoai.
7
MOT SO KHAI NIEM C BAN
He ong the la he co cac tnh chat hoa hoc va vat ly
giong nhau trong toan bo the tch cua he.
He d the la he co be mat phan chia cac phan cua he
thanh nhng phan co tnh chat hoa hoc va vat ly khac
nhau.
Pha la phan ong the cua he d the co thanh phan , cau
tao , tnh chat nhat nh va c phan chia vi cac phan
khac bang be mat phan chia nao o.
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MOT SO KHAI NIEM C BAN
Nhiet dung (C) cua mot chat la lng nhiet can dung e nang nhiet o cua mot
lng xac nh chat o len mot o.
Nhiet dung rieng la lng nhiet can dung e nang mot gam chat o len mot o.
Nhiet dung phan t la lng nhiet can dung e nang mot mol chat o len mot o.
Nhiet dung ang ap la nhiet dung cua qua trnh nang nhiet trong ieu kien ang ap,
ky hieu C
P
.
Nhiet dung ang tch la nhiet dung cua qua trnh nang nhiet trong ieu kien ang tch,
Ky hieu C
V
. oi vi kh ly tng, xet cho 1 mol kh th: Cp=5R/2 ; Cv =3R/2; vi
R=8,3145 J/mol. o
V du : Nhiet dung rieng ang ap cua nc trong khoang 14,5
0
C 15,5
0
C bang 1 cal
/ g.o , nhiet dung phan t ang ap cua nc trong khoang nhiet o nay la
18,015 cal/mol. o.
9
NANG LNG
La thc o o van ong cua vat chat. ng vi nhng hnh thai
van ong khac nhau cua vat chat chung ta co nhng hnh thai nang
lng khac nhau nh the nang, ong nang, noi nang.

Hai dang the hien cua nang lng o la NHIET, va CONG

Lu y: khong co gia tr nang lng bang 0 tuyet oi ma ch co
nang lng bang 0 ng vi mot he quy chieu chuan nao o.
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n v o nang lng

Theo he SI la Joule (J):
oi khi dung n v calorie:
1 cal = 4.184 J
n v Calory dinh dng (Cal) (nutritional Calorie):
1 Cal = 1000 cal = 1 kcal
( )( )
J 1
s / m kg 1
m/s 1 kg 2
2 2
2
2
1
2
2
1
=
=
= = mv E
k
11
NHIET
Nhiet (q) la thc o s chuyen ong hon loan (
chuyen ong nhiet) cua cac tieu phan tao nen chat
hay he.


12
CONG
Cong (w) la thc o s chuyen ong co trat t va co
hng cua cac tieu phan theo hng cua trng lc

CONG (W) = tch cua lc (F)tac dung len vat lam vat di
chuyen mot quang ng d
w = F d
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NOI NANG
Noi nang (U) (Internal Energy) cua he la nang lng co
san , an dau ben trong he , bao gom nang lng chuyen
ong tnh tien , chuyen ong quay cua cac phan t ,
chuyen ong quay va chuyen ong giao ong cua cac
nguyen t va nhom nguyen t ben trong phan t va
tinh the, chuyen ong cua electron trong nguyen t , nang
lng ben trong hat nhan.

14
Nang lng cua he: bao gom tong cua ong
nang, The nang, va Noi nang cua he.
oi vi cac phan ng hoa hoc, s bien oi
ong nang va the nang cua he la khong ang
ke do o ta ch quan tam en Noi nang.
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NGUYEN LY TH NHAT CUA NHIET ONG HOC
Neu trong qua trnh nao o ma co mot dang nang
lng a mat i th thay cho no phai co mot dang
nang lng khac xuat hien vi lng tng ng
nghiem ngat.

(nh luat bao toan nang lng)
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Moi lien he gia Nhiet va Cong
Nang lng khong t sinh ra va khong t mat i
Nang lng cua (he thong + moi trng) la mot hang so
Khi mot he b bien oi (vat ly hay hoa hoc), noi nang cua he
thay oi tuy thuoc vao lng nhiet va cong he trao oi vi moi
trng. :
DU = q + w
NGUYEN LY TH NHAT CUA NHIET ONG HOC
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q:
+ khi he thu nhiet t moi trng ngoai,
khi he toa nhiet ra moi trng ngoai
w:
+ khi he b moi trng ngoai tac dung len cong w,
khi he tac dung cong w len moi trng ngoai.
Qui c ve dau
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19
Cong gian n
Cong w khi he chuyen t trang thai 1 sang trang thai 2
se la :
w = - PAV = - P ( V
2
V
1
)
Trong o P la ap suat cua he , V
1
la the tch cua he
trang thai 1 , V
2
la the tch cua he trang thai 2.
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Qua trnh ang tch (Av=0)
Trong trng hp cac qua trnh dien ra ieu kien the tch
khong oi
(V = const) th w = 0 , suy ra:

q
v
= A U = U
2
U
1

Toan bo nhiet nang ma he thu vao trong qua trnh ang
tch dung e lam tang noi nang cua he.
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Qua trnh ang ap (P=const)
w= -PAV do o:
q
p
= AU + PAV =( U
2
U
1
) + P (V
2
V
1
) = (U
2
+ PV
2
) (U
1

+ PV
1
)
Ngi ta at :
H = U + PV
Va goi H la Enthalpy. Vay enthalpy la mot ham phc tap
gom noi nang (U) cua he cong vi tch ca the tch (V)
cua he va ap suat (P) at tren he.

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ENTHALPY
Khi cung cap cho he mot lng nhiet q th trong trng hp tong quat
nhiet nang nay se c dung e lam tang noi nang ( phan noi nang
tang them ky hieu la AU) va e thc hien cong w chong lai cac lc
ben ngoai tac dung vao he.
nh luat th nhat cua nhiet ong hoc co the bieu dien bang bieu
thc toan hoc sau :
q = AU - w = ( U
2
U
1
) w
Trong o , cong w oi vi cac qua trnh (chu yeu la cong chong ap
suat ben ngoai) , U
1
la noi nang cua he trc khi c cung cap nhiet
, U
2
la noi nang cua he sau khi a c cung cap nhiet
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ENTHALPY
Goi H
1
la enthalpy cua trang thai ban au cua he , H
2
la
enthalpycua trang thai cuoi cung cua he th chung ta thu
c cong thc
q
p
= H
2
H
1
= AH
Nh vay AH la hieu ng nhiet cua cac qua trnh hoa hoc
trong ieu kien ap suat khong oi ( ieu kien ang ap).
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ENTHALPY
Neu trong qua trnh he thu nhiet cua moi trng th Enthalpy cua he
tang len tc la
H2 > H1 AH = H2 H1 > 0
Neu trong qua trnh he toa nhiet ra moi trng th Enthalpy cua he
giam xuong tc la
H2 < H1 AH = H2 H1 < 0
V du:
C + O
2
= CO
2
AH = -396 kJ phan ng toa nhiet
2 HCl = H
2
+ Cl
2
AH = +184 kJ phan ng thu nhiet
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MOI QUAN HE GIA ENTANPI VA NOI NANG.

oi vi nhng qua trnh ch co chat ran va long tham gia th ai
lng AV co gia tr khong ang ke , do o khi nhng qua trnh
nay c thc hien ap suat thap th :
AH ~ AU
Cong thc tren cho thay nhiet truyen cho chat ran va long chu
yeu chuyen thanh noi nang ma khong sinh cong, tc la chu yeu
lam tang nhiet o cua he.
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MOI QUAN HE GIA ENTANPI VA NOI NANG
oi vi nhng qua trnh co chat phan ng hay san pham phan ng
the kh th AH va AU co the khac xa nhau.
Vi chat kh :
PAV = AnRT
Trong o An la hieu so phan t gam cua cac san pham kh vi so
phan t gam cua cac chat kh tham gia phan ng .
Nh vay :
AH = AU + AnRT
T ay , khi An = 0 th AH = AU , nhng khi An = 0 th AH = AU.
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DH = H
cuoi
- H
au
= q
P
Enthalpy
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Qua trnh thu nhiet va toa nhiet
Thu nhiet:: hap thu nhiet t moi trng.
Vd: qua trnh bay hi cua chat long
Toa Nhiet: toa nhiet ra moi trng

Vd: Hoa tan H
2
SO
4
trong nc
Phan ng chay cacbon
NGUYEN LY TH NHAT CUA NHIET ONG HOC
30


CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g) AH = -802 kJ
2CH
4
(g) + 4O
2
(g) 2CO
2
(g) + 4H
2
O(g)
AH = -1604 kJ
CO
2
(g) + 2H
2
O(g) CH
4
(g) + 2O
2
(g) DH = +802 kJ
H
2
O(g) H
2
O(l) DH = -88 kJ
Entanpi cua phan ng hoa hoc
31

Phng phap o nhiet lng
32

DH = q
P

q
p
= -q
dung dch

= -(nhiet dung cua dung dch) (so gam
dung dch) DT.
Nhiet lng ke ang ap
33
q
p
= -C
nhiet lng ke
T
Bomb Calorimetry
Nhiet lng ke ang tch
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TNH TOAN HIEU NG NHIET CUA
PHAN NG HOA HOC
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NH LUAT HESS
Hieu ng nhiet cua qua trnh hoa hoc
ch phu thuoc vao ban chat va trang
thai cua cac chat au va san pham
cuoi ch khong phu thuoc vao ng i
cua qua trnh
36
V du:
T Cacbon va Oxy co the ieu che CO
2
theo hai cach
Cach 1: ot chay trc tiep cacbon
C (than ch) + O
2
(kh) = CO
2
(kh) AH = -393,5 kJ
Cach 2: tien hanh qua hai giai oan
C (than ch) + O
2
(kh) = CO (kh) AH
1
= -110,5 kJ
CO (kh) + O
2
(kh) = CO
2
(kh) AH
2
= - 283,0 kJ
Ta co AH = AH
1
+ AH
2

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HE QUA CUA NH LUAT HESS
He qua 1:
Nhiet phan huy cua 1 hp chat co gia tr tuyet oi ung bang nhiet
hnh thanh cua hp chat o nhng ngc dau.
V du:
H
2
(kh) + O
2
(kh) = H
2
O (long) co AH = -268 KJ
Vay nhiet hnh thanh cua H
2
O la AH
0
f = - 268 KJ/mol
Nhiet phan huy cua H
2
O (long) thanh H
2
(kh) + O
2
(kh) la +268
KJ/mol
38

AH
1
= AH
2
+ AH
3


39
e s oi chieu c thong nhat ngi ta chon nhng ieu kien sau
ay la ieu kien chuan:
Ap suat c chon la 1 atm =760 mm Hg (hoc 1 bar =10
5
Pa v
ap suat nay neu nhiet o u cao kh co the xem nh ly tng)
Cac chat c lay trang thai nguyen chat va ben nhat
298,15 K va 1 atm.
Hau het cac d lieu nhiet ong c ghi nhan tai nhiet o 298
K (chnh xac hn la 298,15 K). Tuy nhien nhiet o khong c bao
gom trong khai niem trang thai chuan. Chung ta co the thiet
lap trang thai chuan bat c nhiet o nao.
40
Phng trnh nhiet hoa hoc:
Mot phng trnh nhiet hoa hoc phai bao gom:
Phng trnh phan ng hoa hoc
Trang thai hoa chat ( ran, long, kh,)
ieu kien th nghiem ( nhiet o, ap suat,)
Nhiet lng trao oi trong phan ng q
p
hay q
v
.
Chu y: Nhiet lng trao oi trong phan ng bao gi cung tng
ng vi gia thiet la phan ng xay ra hoan toan khong kem
theo phan ng phu.
41
V du:
C (r) + 1/ 2 O
2
(k) CO(k) AH
o
298K
=-110.5 kJ
ngha la 1 mol cacbon ran tac dung vi mol oxygen tao 1 mol kh
monoxyt cacbon; Nhiet phan ng 1 bar, 298.15 K la 110.5 kJ ( nhiet
phan ng toa ra la 110.5 kJ).
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Enthalpy mol chuan thc ( sinh nhiet mol, nhiet tao thanh mol
chuan-heat of formation) AH
o
f
Enthalpy mol chun thccua mot hp chat la hieu ng nhiet cua phan
ng tao thanh 1 phan t gam (1 mol) chat o t cac n chat ben
ieu kien tieu chuan.
Lu y: ngi ta quy c
Enthalpy (AH
0
f
) cua cac n chat ben ieu kien tieu chuan co gia
tr bang 0.

43
4C (r) + 6 H
2
(k) + O
2
(k) 2 C
2
H
5
OH(l)
AH
o
= -555,38 kJ


Vay: A H
o
f
(C
2
H
5
OH,l) = -555,38 kJ / 2 mol
= -277,69 kJ.mol
-1

44
NHIET TAOTHANH (AH
0
f
)
Nhiet tao thanh cua cac n chat ben = 0
45
Thieu nhiet mol chuan (nhiet ot chay-heat of combustion) AH
o
c
Thieu nhiet mol chuan (nhiet ot chay) la hieu ng nhiet cua phan
ng ot chay hoan toan 1 mol chat bang oxygen ieu kien chuan.
C
6
H
12
O
6
(aq) + 6 O
2
(k) 6 CO
2
(k) + 6 H
2
O(k)
AH
o
=-2816 kJ
Nhiet ot chay cua ng glucoz la:
AH
o
c
=-2816 kJ.mol
-1
Lu y: Trong phan ng chay hoan toan cua cac hp chat hu c,
carbon tao thanh CO
2
, Hydro tao thanh H
2
O, Nit tao thanh N
2


46
Xet phan ng :
C (r) + O
2
(k) CO
2
(k) AH
o
298 K
=-393.5 kJ
Vay nhiet ot chay cua cacbon tai ieu kien chuan va nhiet o 298 K
la
(AH
o
c
)
298 K [C(r)]
= -393.5 kJ.mol
-1

Xet phan ng :
CO (k) + 1/2 O
2
(k) CO
2
(k) AH
o
298 K
=-283.0 kJ
Vay nhiet ot chay cua monoxyt cacbon tai ieu kien chuan va nhiet
o 298 K la
(AH
o
c
)
298 K [CO(k)]
= -283.5 kJ.mol
-1
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Tnh toan Nhiet phan ng AH
o
r
bang nhiet tao
thanh AH
o
f

He qua 2 (nh Luat Hess)
Hieu ng nhiet cua phan ng hoa hoc bang tong nhiet
hnh thanh cua cac san pham tr i tong nhiet hnh thanh
cua tac chat
AH
o
r
= EnAH
o
f
san pham - EnAH
o
f
tac chat
48
AH
p
= AH
1
+ AH
2
+ AH
3

Tnh toan Enthalpi phan ng bang enthalpi hnh thanh
Ap dung nh luat Hess
49
Tnh toan Nhiet phan ng AH
o
r
bang nang lng lien ket
AH
o
r
= E Nang lng t noi - E Nang lng rap noi
V du: Tnh AH
o
r
cua phan ng
C
2
H
4
(k) + H
2
(k) C
2
H
6
(k) AH
o
r=?
AH
o
r=1 mol E
H-H
+ 1 mol E
C=C
+ 4 mol E
C-H

(6 mol E
C-H
+1 mol E
C-C
)

=1mol(435 kJ.mol
-1
)+1mol(598 kJ.mol
-1
)
-2 mol(416 kJ.mol
-1
)-1 mol(356 kJ.mol
-1
)
= -155 kJ
So vi ket qua tnh t enthalpy mol chuan thc:
AH
o
r =1 mol AH
o
f
, C
2
H
6
(k) 1 mol AH
o
f, C
2
H
4
(k)
=-84.67 kJ- 52,28 kJ
= -136.95 kJ. Vay ket qua nao ang tin cay hn?
50
CAC NGUON NANG LNG TRONG
T NHIEN
51
THC PHAM
Thc pham cung cap nang lng cho con ngi chu yeu dang
cacbonhydrat (gao, bot m) va m.
Trong c the, cacbonhydrat b chuyen hoa thanh ng glucoz. ng cung
cap nang lng cho c the qua phan ng:
C
6
H
12
O
6
(aq) + 6O
2
(g) 6CO
2
(g)+ 6H
2
O(l)
DH = -2816 kJ AH
o
c
(C
6
H
12
O
6
, aq) =?
Nang lng d tr trong c the di dang m. M cung cap nang
lng cho c the qua phan ng:
2C
57
H
110
O
6
+ 163O
2
114CO
2
+ 110H
2
O
DH = -75,520 kJ AH
o
c
= ?
52
Gia tr nang lng cua mot so thc pham
53
CAC DANG NHIEN LIEU THONG DUNG
54
Gia tr nang lng cua mot so dang nhien lieu
55
Chieu xay ra cua cac bien oi t nhien.
Nguyen ly II cua nhiet ong hoc. Entropy S
56
Trong phan trc chung ta a tra li cau hoi:" Neu mot phan ng
hoa hoc t xay ra no se toa nhiet hay thu nhiet?"

Nhng con mot cau hoi c ban hn na la:"Neu e t nhien, khong
co s tac ong nao t moi trng, lieu mot phan ng co xay ra
hay khong?"
V du: Phan ng CH
4
+ O
2
CO
2
+ H
2
O tai sao trong
t nhien khong thay chieu ngc lai?

Vay: mot bien oi t nhien th co HNG XAC NH
57
Bien oi t nhien (spontaneous change)
La mot bien oi xay ra c mot cach t nhien ma khong can
tac ong cua yeu to ben ngoai.
Mot bien oi t nhien khong nhat thiet phai xay ra nhanh.
Chieu cua bien oi t nhien co the phu thuoc vao nhiet o (
Tai T>0
o
C, nc a hoa long t nhien. Tai T<0
o
C, nc hoa ran
t nhien
Trong mot bien oi t nhien, ng bien oi cua san pham va
tac chat la bien oi bat thuan nghch (irreversible)
58
59
Vay
Ch da vao s bien oi noi nang (hay Enthalpy AH) th
khong the tien oan c chieu phan ng.

e tien oan chnh xac chieu hng cua phan ng ta
can phai xem xet mot yeu to na o la O MAT
TRAT T cua he (c the hien qua gia tr ENTROPY ky
hieu S)
60
61
62
63
NGUYEN LY 2
Trong ieu kien nang lng khong oi, he co khuynh hng
chuyen t trang thai co o mat trat t thap sang trang thai
co o mat trat t cao hn.

Hay:
Khong the co qua trnh t chuyen nang lng t vat the co
cac tieu phan chuyen ong trat t sang vat the co cac tieu
phan chuyen ong kem trat t hn.
64
ENTROPI
Entropi S la thc o o hon loan cua trang thai cua he thong
Bien oi xay ra t nhien th i kem vi s tang entropy
Thng th s gia tang entropy cua mot qua trnh se di cung vi
s giam entropy cua qua trnh khac nhng s gia tang la lan at
Entropy la mot ham trang thai
Cho 1 he thong: AS = S
final
- S
initial
.
Neu AS > 0 he thong mat trat t hn
AS < 0 he thong trat t hn


65
Trong nhiet ong hoc, s hon loan cua mot he thong c o bang
entropy S.
Neu nh noi nang U xac nh lng cua nang lng th entropy S
xac nh nang lng nay c cat gi ra sao.
Entropy thap ngha la t hon loan, entropy cao ngha la hon loan
nhieu.
Khong co khai niem entropy am tc entropy luon luon >=0.
66
Entropy cua mot chat co the tang bang hai cach:
Tang bang cach cung cap nhiet dan en gia tang chuyen ong tc
la tang s hon loan cua cac phan t.
Tang bang cach cung cap nhieu cho hn e cac phan t co the
phan tan de dang hn.
67
Mot so quy tac e danh gia s bien thien cua entropy S trong cac qua
trnh hoa hoc:
S
o
tang (AS
o
>0) khi cac chat chuyen t trang thai ran sang long hay
kh.
V du: H
2
O (r) H
2
O (l) AS
o
>0
S
o
tang (AS
o
>0) khi mot chat ran hay long hoa tan vao nc hay dung
moi.
S
o
giam (AS
o
<0) khi mot chat kh hoa tan vao nc hay dung moi.
S
o
tang khi M (khoi lng phan t) tang.
V du: S
o
O2
< S
o
O3
68
S
o
giam chat ran mang lien ket cong hoa tr, S
o
tang khi
lien ket co mot phan tnh kim loai.
V du: S
o
C(diamond) < S
o
C(graphite)
S
o
tang ty le vi o yeu va o mem cua lien ket gia
cac nguyen t.
S
o
tang theo o phc tap cua phan t.
69
Tnh chat cua entropi
1. Moi chat co gia tr entropi rieng cua mnh , phan t cang phc tap
th entropi cang ln.
2. Entropi cua moi chat 0 K eu bang 0 v chung ch con mot trang
thai sap xep duy nhat (W=1).
3. Entropi cua cac chat tang theo s tang cua nhiet o.
4. Entropi la mot ham trang thai do o s tang entropi cua mot qua
trnh tnh theo cong thc:
AS
o
r
= EnS
san pham
- EnS
tac chat
70
Entropy mol chuan thc (S
0
298
)
La gia tr Entropy cua 1 mol chat o ieu kien ieu kien
tieu chuan co ap suat 1 atm (760 mm Hg), va nhiet o
bang 25
o
C (298.15K)

n v tnh cua S
0
298
la cal/mol.K hoac J/mol.K

Gia tr nay co the tra cu c t cac SO TAY HOA
HOC.
71
V du
Tnh AS
0
298
cua phan ng
C
(than )
+ O
2 (kh)
= CO
2 (kh)
Biet giatrEntropy cua cac chat nh sau
Chat C
(than )
O
2 (kh)
CO
2 (kh)

S
0
298
(Cal/ mol. oK) 1.37 49 51.06

AS
0
= 1mol x S
0
(CO
2
) [1 mol x S
0
(C) + 1 mol x S
0
(O
2
)]
AS
0
= 1mol x 51.06 Cal/ mol. oK [1 mol x 1.37 Cal/ mol. oK + 1
mol x 49 Cal/ mol. oK
AS
0
= 0.69 Cal/ oK
Nh vay omat trat tcua hetang len sau phan ng.
72
Anh hng cua moi trng:
AStong cong = AShe thong + ASmoi trng
ASmoi trng ty le thuan vi lng nhiet toa ra t he thong (-
AH) va ty le nghch vi nhiet o T. Tai ap suat khong oi, ta
co the viet :
ASmoi trng= -AH/ T
tc la: AStong cong = AShe thong- AH/ T
73
V du:
Phan ng 2 Mg (r) + O2 (k) 2 MgO(r)
co AS
o
r = -217 J.K
-1
.mol
-1
<0
Tuy nhien phan ng van xay ra c v AH
o
r<<0 (AH
o
r=-1202 kJ.mol
-1
).
Ta co:
AStong cong = AShe thong - AH/ T
= -217 J.K
-1
.mol
-1
+ 1202.103 J.mol
-1
/298 K
= 3.81.103 J.K
-1
.mol
-1
>0
74
Nguyen ly II cua nhiet ong hoc cung co the c phat bieu
nh sau
" Mot bien oi t nhien th kem theo s tang
tong entropy cua he thong va moi trng cua
no."
75
Giai thch khai niem entropy mc o phan t (The
Molecular Interpretation of Entropy)
There are three atomic modes of motion (chuyen ong):
Translation-tnh tien (the moving of a molecule from one
point in space to another),
Vibration - dao ong (the shortening and lengthening of
bonds, including the change in bond angles),
Rotation - xoay (the spinning of a molecule about some
axis).
76
Energy is required to get a molecule to translate, vibrate or rotate.
The more energy stored in translation, vibration and rotation, the greater the
degrees of freedom and the higher the entropy.
In a perfect crystal at 0 K there is no translation, rotation or vibration of
molecules. Therefore, this is a state of perfect order.
Third Law of Thermodynamics: the entropy of a perfect crystal at 0 K is zero.
Entropy changes dramatically at a phase change.

77
78
Nang lng t do G (Free Energy)
AStong cong = AShe thong- AH/ T
Hay: -TAStong cong = AH - TAShe thong
Biu dien khai niem bien oi cua entropy tong bang mot ai lng
goi la nang lng t do Gibb: AG = -TAStong cong (*)
Ta co: AG = AH - TAS
Nh vay, thay v xem xet s bien oi cua entropy tong cong cua ca he
thong va moi trng xung quanh, nay ta ch xet s bien oi cua nang
lng t do G cua ban than he thong e d oan mot bien oi co
xay ra t nhien hay khong.
79
Dau tr (-) * cho thay nang lng t do giam khi entropy
tong cong tang. Nh vay, tai ap suat va nhiet o khong
oi, chieu cua mot bien oi t nhien la chieu lam giam
nang lng t do.
80
Bien oi enthalpy Bien oi entropy Bien oi xay ra t nhien?
---------------------------------------------------------------------------------------------
Toa nhiet (AH<0) Tang (AS>0) Co, AG<0
Toa nhiet (AH<0) Giam (AS<0) Co, neu ,TAS, < ,AH,,
AG<0
Thu nhiet (AH>0) Tang (AS>0) Co, neu TAS> AH,
AG<0
Thu nhiet (AH>0) Giam (AS<0) Khong, AG>0
_______________________________________________________
81
V du: Qua trnh ong ac cua nc tai 0oC(273.15 K) va 1 atm co
AH = -AHnc = -6.00 kJ.mol
-1
AS = -ASnc = -21.97 J.K
-1
.mol
-1
= -21.97.10-3 kJ.K
-1
.mol
-1

The cac gia tr tren vao bieu thc cua AG:
AG = AH - TAS
Ta co: AG = -6.00 kJ.mol
-1
1- {(273.15 K) (-21.97.10-3 kJ.K
-
1
.mol
-1
1)}
= 0.00 kJ.mol
-1

Nh vay: Mot phan ng can bang tai nhiet o va ap suat khong
oi co AG=0
ieu nay cho phep ta d oan c nhiet o soi, nhiet o nong
chay cua cac chat.
82
Nang lng t do chuan thc AG
o
f
(standard free
energy of formation)
La bien thien nang lng t do cua qua trnh tao thanh 1 mol chat
ieu kien tieu chuan (25
0
C, 1 atm) xuat phat t cac n chat ben.
n v cua AG
0
f
la Kcal/mol hoac KJ/mol
Cac n chat ben ieu kien tieu chuan co AG
0
f
= 0
Gia tr AG
0
f
cua cac chat c xac nh bang thc nghiem.
Co the tra cu cac ai lng AG
0
f
trong cac so tay hoa hoc.
83
Tnh AG

cua cac phan ng hoa hoc t AG
0
298
cua cac hp chat

V du: tnh AG
0
cua phan ng
C
(than )
+ O
2 (kh)
= CO
2 (kh)
Biet giatrEntropy cua cac chat nh sau
Chat C
(than )
O
2 (kh)
CO
2 (kh)

AG
0
298
(KCal/ mol). 0 0 -94.25

AG = EAGsan pham - EAGtac chat
AG
0
= 1mol x AG
0
(CO
2
) [1 mol x AG
0
(C) + 1 mol x AG
0
(O
2
)]
AG
0
= 1mol x 94.25 KCal/ mol [1 mol x 0 KCal/ mol + 1 mol x 0 Kcal/ mol
AG
0
= -94.25 Kcal
Nh vay phan ng txay ra theo chieu thuan.
84
Nang lng t do chuan thc AG
o
f
chnh la thc o o ben
tng oi cua mot hp chat so vi cac nguyen to tao thanh
no.
Neu AG
o
f
<0 tai mot nhiet o xac nh th co ngha la cac
nguyen to co khuynh hng t nhien tao thanh hp chat tai
nhiet o o tc tai ieu kien chuan hp chat nay la ben
hn cac nguyen to tao thanh nen no.
Con neu AG
o
f
>0 th ieu ngc lai se xay ra, hp chat co
khuynh hng t nhien la phan huy tr lai thanh cac nguyen
to.
85
y ngha cua AG
p
AG
p
c dung lam thc do cho kha nang t dien bien
cua mot phan ng hoa hoc
AG
p
< 0 qua trnh hoa hoc co kha nang t dien bien.
AG
p
> 0 qua trnh hoa hoc khong co kha nang t
dien bien.
AG
p
= 0 he hoa hoc nam trang thai can bang.
86
VAI TRO CUA AH, AS, T OI VI DAU CUA AG VA CHIEU CUA QUA
TRNH.
Neu AH <0 & AS> 0
AG <0
qua trnh chac chan xay ra theo chieu thuan.
Neu AS~0
muon cho AG < 0 phai co AH <0
qua trnh t xay ra theo chieu phat nhiet.
87
VAI TRO CUA AH, AS, T OI VI DAU CUA AG VA CHIEU CUA QUA
TRNH.
Neu AH < 0 & AS <0
Muon cho AG <0 th : |AH| > |TAS|.

Nhiet o co anh hng manh en chieu cua qua
trnh:
nhiet o thap : |TAS| nho nen de xay ra ieu kien |AH| >
|TAS| qua trnh t xay ra theo chieu thuan.
nhiet o cao : |TAS| ln nen de xay ra ieu kien |AH| <
|TAS| qua trnh t xay ra theo chieu nghch.

88
VAI TRO CUA AH, AS, T OI VI DAU CUA AG VA CHIEU CUA QUA
TRNH.
Neu AH>0 va AS>0
Muon cho AG<0 th : |AH| < |TAS|.
nhiet o gi vai tro quan trong:
nhiet o cao: |TAS| u ln |AH| < |TAS| AG <0
phan ng theo chieu thuan
nhiet o thap |TAS| khong u ln
|AH| > |TAS| AG >0 phan ng theo chieu Nghch
89
VAI TRO CUA AH, AS, T OI VI DAU CUA AG VA CHIEU CUA QUA
TRNH.
Neu qua trnh co AH>0 va AS <0 th bat ky nhiet o
nao ta cung co AG >0 phan ng khong the xay ra theo
chieu thuan ma ch xay ra theo chieu nghch
90
Tnh hang so can bang K
Ta co: AG
r
= AG
o
r + RT lnK
Tai can bang: 0 = AG
o
r + RT lnK
hay AG
o
r= RT lnK
V du: Tnh Kp tai 25
o
C cho can bang sau
N
2
O
4
(k) 2 NO
2
(k)
Ta co: AG
o
r = 2 AG
o
r (NO
2
,k) - AG
o
r(N
2
O
4
,k)
= 2 51.31 97.89 kJ.mol
-1

= +4.73 kJ.mol
-1

Ma ln Kp = -AG
o
r / RT
= -(4.73 kJ.mol
-1
/ 2.4790 kJ.mol
-1
) = -1.91
Suy ra Kp = 0.15

91
BAI TAP AP DUNG
92
1 J = 1 N.m= 1 Pa.m
3
= 1 kg. m
2
. s
-2
1 erg = 10
-7
J
1 cal = 4,184 J
1 eV = 1,6021892 x 10
-19
J
L.atm = 101,325 J
cm
-1
= 1,986477 x 10
-23
J

1 Pa = 1 N.m
-2
= 1 kg. m
-1
. s
-1

1 bar = 105 Pa
1 atm = 101,325 Pa
1 atm = 760 torr
1 psi = 6897, 7572 Pa

93
R = 8,31441 J.K
-1
mol
-1

= 8,31441 m
3
. Pa.K
-1
.mol
-1

= 0,0831441 L.bar. K
-1
.mol
-1

= 0,0820568 L.atm.K
-1
.mol
-1
94
Bai 1
Mot qua bong bay cha khong kh co the tch 4,00x10
6
lt.
Cung cap mot lng nhiet 1,3 x 10
8
J cho qua bong bang
cach ot nong th thay qua bong tang the tch len thanh
4,5 x 10
6
lt. Hay tnh s thay oi noi nang cua qua bong
biet rang trong qua trnh gian n qua bong luon chu mot
ap suat khong oi t kh quyen khong kh la 1,0 atm.
95
Li giai
Noi nang AU c tnh theo phng trnh: AU= q + W
vi q la lng nhiet cung cap vao he : q = 1,3 x 10
8
J
Cong trong trng hp nay la cong gian n do he tac ong len moi trng nen:
W = - PAV = - 1 atm x (4,5x10
6
Lit 4,0x10
6
Lit)= -5,0x10
5
Lit atm
oi n v : 1 Lit atm = 101,3 J ta co
W = -5,0x10
5
Lit atm x 101.3 J/Lit atm = -5,1x10
7
J
Vay: AU= q + W = 1,3 x 10
8
J + (-5,1x10
7
J) = 8x10
7
J
Nh vay do lng nhiet cung cap vao he ln hn lng cong do he tac ong len
moi trng nen noi nang cua he tang len.
96
Bai 2
Khi 1 lt dung dch Ba(NO
3
)
2
1M 25
0
C c tron lan vi 1 lt dung
dch Na
2
SO
4
1M 25
o
C trong mot nhiet lng ke ta thay trong nhiet
lng ke xuat hien chat ket tua mau trang BaSO
4
ong thi nhiet
o cua nhiet lng ke tang t 25
0
C len ti 28,1
o
C. Hay tnh s bien
oi entalpi cua qua trnh hnh thanh 1 mol BaSO
4
biet rang dung dch
co t trong l1 1g/ml va co nhiet dung rieng la 4,18 J
o
C
-1
g
-1
. Gia s
lng nhiet hap thu bi nhiet lng ke la khong ang ke.
97
Li giai
Khi tron lan hai dung dch , phan ng xay ra la:
Ba
2+
(dung dch
)

+ SO
4
2-
(dung dch)
= BaSO
4

(ran)
Do nhiet ocua dung dch tang len nen ay laphan ng toa nhiet; AH

codau am
ay labien oi ang ap do osbien oi entalpi chnh lahieu ng nhiet cua phan ng:
AH = q
maq = nhiet toara bi phan ng = nhiet hap thu bi dung dch = (nhiet dung rieng cua
dung dch)x(khoi lng dung dch)x(otang tang nhiet o)

nhiet hap thu bi dung dch= (4,14 J
o
C
-1
g
-1
)x(2 x10
3
g)x(28,1
o
C

25
o
C) = 2,6 x10
4
J

Nh vay khi 1 mol BaSO
4
c hnh thanh th lng nhiet toa ra la2,6 x 10
4
J
Vay: AH = - 2,6 x10
4
J/mol = -26 kJ/mol
98
Bai 3
Khi 2 mol kh SO
2
phan ng hoan toan vi 1 mol kh O
2
e
tao thanh 2 mol kh SO
3
25
o
C tai ap suat khong oi la 1
atm th toa ra mot lng nhiet la 198 kJ. Hay tnh AH va
AU cho qua trnh bien oi.
99
Li giai
Bai giai:
SO
2
+ O
2
= SO
3

Somol kh trc phan ng : 2 mol 1 mol 0 mol n
trc
= 3 mol
Somol kh sau phan ng: 0 mol 0 mol 2 mol n
sau
= 2 mol
An = n
sau
- n
trc
= - 1 mol

ieu kien ang ap AH= q = -198 kJ (dau thehien quatrnh toa nhiet)
AU = q + w
Vi w = -PAV= ( ) ( ) kJ K
Kmol
J
mol nRT
P
RT
n 48 , 2 298 3145 , 8 1 =
|
.
|

\
|
= A =
|
.
|

\
|
A
Vay: AU = q + w = -198 kJ + 2,48 kJ = -196 kJ

Nhan xet AU vaAH khac nhau do costhay oi vethetch cua hekhi phan ng xay ra
(cong c thc hien tmoi trng ngoai vao he)
100
Bai 4
Hay tnh AH
0

cho phan ng ot chay NH
3
nh sau:
4NH
3
(k) + 7O
2
(k) = 4 NO
2
(k) + 6 H
2
O

(l)
101
Li giai

Chat
NH
3
(k) NO
2
(k) H
2
O (l) Al
2
O
3
(r) Fe
2
O
3
(r) CO
2
(k) CH
3
OH (l) C
8
H
18
(l)
AH
0
f
(kJ/mol) -46 34 -286 -167 -826 -349 -239 -269
Bai giai:






AH
0
phan

ng
= AH
0
(a)
+ AH
0
(b)
+AH
0
(c)
+AH
0
(d)

= 4 (-AH
0
f (NH3)+
) + 0 + 4(AH
0
f (NO2)
) + 6(AH
0
f (H2O)
)
= AH
0
f (san pham)
- AH
0
f (tac chat)

AH
0
phan

ng
= 6(-286 kJ) + 4(34kJ) 4(-46 kJ) = -1369 kJ
4NH
3
(k)

7O
2

2N
2
(k) + 6 H
2
(k)

7 O
2
(k)
4NO
2
(k)

6H
2
O (l)
AH
0
(a)

AH
0
(b)
=0
AH
0
(c)

AH
0
(d)

102
Bai 5
Cho cac solieu sau:
H
2
(k) + O
2
H
2
O (l) AH
0
= -285,8 kJ
N
2
O
5
(k) + H
2
O (l) 2HNO
3
(l) AH
0

= -76,6 kJ
N
2
(k) + 3/2 O
2
+ H
2
HNO
3
(l) AH
0

= -174,1 kJ
Hay tnh AH
0

cua phan ng:
2N
2
(k) + 5O
2
(k) 2N
2
O
5
(k)
AH
0

= 28,4 kJ
103
Bai 6
Quy trnh Oswald dung eieu cheHNO
3
tNH
3
trong cong
nghiep bao gom cac bc sau:
4NH
3
(k) + 5O
2
(k) 4 NO (k) + 6H
2
O

(k)
2NO (k) + O
2
(k) 2 NO
2
(k)
3NO
2
(k) + H
2
O (l) 2 HNO
3
(dd) + NO (k)
a) Hay tnh AH
0
cho moi quatrnh tren da vao giatrAH
0
f

cua cac hp chat (tra c trong sotay hoa hoc)
b) Viet phan ng tong quat cua quatrnh ieu chetren. Qua
trnh tong quat nay toanhiet hay thu nhiet?

a. AH
0
1
= -908kJ ; AH
0
2
= -112 kJ ; AH
0
3
= -140 kJ ; b. toa nhiet
104
Bai 7
Xet cac quatrnh bien oi sau:
a) H
2
O (k) H
2
O (l)
b) H
2
(k) + Cl
2
(k) 2HCl (k)
c) 2H
2
(k) + O
2
(k) 2H
2
O (k)
d) Xe (k) + F
2
(k) XeF
2
(r)
e) NiCl
2
.6H
2
O (r) NiCl
2
(r) + 6H
2
O (k)
f) CO
2
(r) CO
2
(k)
ieu kien ap suat khong oi, quatrnh naocostac ong
cong theen moi trng ngoai? Quatrnh nao nhan cong
tmoi ttrng ngoai? Quatrnh nao khong costhc hien
cong?
105
Bai 8
Doan dau cua AS
0
cua cac phan ng sau:
a) CaCO
3
(r) CaO (r) + CO
2
(k)
b) 2SO
2
(k) + O
2
(k) 2SO
2
(k)
106
Bai 9
nhiet onao th quatrnh sau t dien ra 1atm:
Br
2
(l) Br
2
(k)
Biet quatrnh nay co
AH
0
= 31,0 kJ/mol vaAS
0
= 93,0 J/mol.o
107
Bai 10
Cho cac solieu sau 25
o
C, 1 atm:
C (kim cng) + O
2
(k) CO
2
(k) AG
0

= -397 kJ
C (than ch) + O
2
(k) CO
2
(k) AG
0

= -394 kJ
Hay tnh AG
0

cua quatrnh
C (kim cng) C (than ch)
Tocho biet than ch hay kim cng ladang thuhnh ben
hn cua Cacbon?

108
Bai 11
Phan ng nao sau ay cothetxay ra ieu kien chuan
25
o
C, 1atm:
a) 2CH
3
OH (l) + H
2
O (l) C
2
H
5
OH (l)
b) O
2
(k) + H
2
(k) H
2
O (l)
c) CO (k) + 2H
2
(k) CH
3
OH (l)
d) NO (k) + O
3
(k) NO
2
(k) + O
2
(k)
109
Bai 12
Tnh AS
0
; AH
0
; AG
0

cho phan ng sau
CaCO
3
(r) CaO (r) + CO
2
(k)
Phan ng nay setdien ra nhiet onao?