CHNG 7

THE ANG AP VA
CHIEU CUA CAC QUA
TRNH HOA HOC

ENTROPI

Da vao nguyen ly 2, nghien cu s

lien he gia lng nhiet ma he thu
vao vi cong ma he thc hien khi
chuyen t nhiet o cao en nhiet o
thap, ngi ta a ra khai niem entropi, S.
Y ngha vat ly:

Entropi la thc o o hon loan trang thai

cua he.
Entropi la thc o xac suat cua trang thai
a cho cua he.
Entropi tieu chuan: S0298, xac nh
250C,1atm, vi kh c xem la ly tng, vi
dung dch th nong o bang mot n v.

Entropi cung nh U, H, la ham trang

thai cua he. Trong qua trnh ma he
thc hien, lng nhiet thoat ra hay
thu vao dung e lam bien thien
entropi.
S = S2 S1 = SC S
Neu qua trnh TN : S = QTN/T
Neu qua trnh bat TN : S = QBTN/T
Tong quat
S Q/T

VI HE CO LAP
Qua trnh TN S = 0
Qua trnh bat TN S > 0

Ngha la entropi tang.

Trong he co lap, nhng qua

trnh t xay ra la nhng qua
trnh co kem theo s tang S.

n v entropi: cal(J)/mol.K

NH LUAT NERNST
(Nguyen ly 3 cua nhiet ong
hoc)
Entropi cua tat ca cac tinh the tinh
khiet 0K eu bang 0.

Vi cac chat khac, nguyen ly phat

bieu nh sau:

Khi mot he tien en 0K, tat ca cac

qua trnh dng lai va entropy cua
he at en cc tieu, tien en 0.

Phan t cang phc tap, S cang

ln.
V du:
S0O = 38.47 , S0O2 = 49.0, S0O3 = 57.08
(cal/mol.K)

Chat cang ran S cang nho

V du 500K :
SBi = 17, SW =11.1, Skimcng=2 (cal/mol.K)

ntrang
thaicuoi
Nhiet o tang ohonloa
th S tang,
nhng p
S SC S R ln
tang th S giam.ohonloa
ntrang
thaiau

S THAY OI ENTROPI VI MOT SO

QUA TRNH

Vi cac phan ng hoa hoc

Vi cac phan ng hoa hoc
ma V>0 S>0 , con khi S<0
V<0.
Tnh s thay oi entropi
S = SC S = Ssan pham - Stac
chat

(Nhan vi he so t lng)

aA + bB = pC + qD
SA

SB

SC

SD

Sp. = cSC + dSD (aSA + bSB)

V du: Vi phan ng
C (gr) + CO2 (k) = 2CO (k)

298K ta co
S0p. = 2S0CO (S0C + S0CO2)
= 2x47.22 (1.37 + 51.06)=
42.01 cal/mol.K

Vi qua trnh chuyen pha, hoa tan

Vi qua trnh TN ang nhiet S =
Q/T
V du: Vi nc a, Qnc O0C la
1436.3 cal/mol.
S = Q/T = 1436.3/273.16 = 5.2583
cal/molK

S phu thuoc cua S vao nhiet

o
V= const
P = const

Q V U
S

T
T
QP H
S

T
T
T2

Ta co

S C P dlnT S2 S1
T1

T2

T2

T1

T1

ST2 ST1 C P dlnT ST2 ST1 C P dlnT

T2
C P const S C P ln
T1
Vi khoang nhiet o nho

THE ANG AP VA CHIEU CUA QUA

TRNH HOA HOC

The ang ap
Xet qua trnh t,p=const, ngi ta
a ra mot ai lng phoi hp
gia H va S, goi la nang lng t
do Gibbs, hay the ang ap ang
nhiet, goi ngan gon la the ang
ap.

G = H TS

G la ham trang thai , n v trung

vi H (kcal(kJ)/mol).

o thay oi G (trong ieu kien t, p

= const) c xac nh:

G = H T S

ay la phung trnh c ban cua

nhiet ong hoa hoc (bang G0
trong SGK).
Con co the ang tch ang nhiet
(V,T = const) hay nang lng t do
Helmholtz.
F = U TS
F = U TS

Tnh G

G = GC G (t le thuan vi
lng chat phan ng).
aA + bB = cC + dD
G 0A

G0B

G0C

G0D

G0p. = c G0C + d G0D (a G0A +

b G0B)

The ang ap tieu chuan cua

cac n chat bang 0.

V du: Cho phan ng

N2 (k) + 3H2 (k) = 2NH3 (k)

298

2S

NH3

298

2H

298

2 G

N2

NH3

00

tt NH
3

3S

H2

00

khoang nhiet o khong

ln lam
0
0
0

298

TS

298

CHIEU DIEN BIEN CUA PHAN

NG THEO G

Theo nguyen ly 1 va 2, ngi ta

chng minh c A -G.

A: Cong co ch ang nhiet.

Qua trnh TN Amax = -G

Phan ng t xay ra A> 0 G<

0.
Phan ng khong xay ra A< 0
G> 0.

Phan ng t xay ra G<0 (H<0, S>0).

Phan ng khong t xay ra G>0 (H>0,
S<0).
ieu kien can bang G=0.
Khi T cang ln th S cang anh hng
en chieu qua trnh.
Khi T nho th H quyet nh chieu qua
trnh.
Neu T trung bnh phai xet G = H
T S

Noi them: khi biet hang so can

bang Kp ta tnh (vi R = 1.987)
G0 = -RTlnKp

Thc nghiem

G< -10 kcal/mol (hay -40 kJ/mol) phan

ng xay ra theo 1 chieu thuan.
G> +10 kcal/mol (hay +40 kJ/mol) phan
ng xay ra theo 1 chieu nghch.
-10 kcal/mol <G< +10 kcal/mol : Phan
ng TN, cang gan 0 cang tien en
can bang.