CHAPTER 17

Spontaneity, Entropy,
and Free Energy
(自發、熵、自由能)

1
 ⾃發
Is it spontaneous?
• At 298K and the standard state of species
…

G
• C(Diamond)  C (Graphite) yes ,
dueto thee
energy
4 GC
• H2O(S)  H2O(l) yes ⼝產物⼀原物

• N2(g) + 3H2(g)  2NH3(g) yes aG 1

| 1 × 0 3× 0
34 Ymol
- =
-

2 x
- -
=

pontaneous
。

aGfo 0
川 Kmol
• How do you judge the spontaneous trend?
Cud ) → [
cg )
dG =
0 × 1 -

3 y
1 = -
3
mol 2

mol
/

4 Gi 3 mol0 k 3 Pontaneous
 GG

Judge the ,
spontaneous trend by free energy
• What is free energy (G)? 單截 Cdiamond ) Ccgraphite) mol
→
dH = 001 - 2 |= - 2

2 GeYotheinic
aHt kYol mol 0

—
0

判斷⾃發/不⾃發
ymol omol
0

aGf 3

• Why can free energy be used to judge the spontaneous trend?

熵 ( 3)
• What is the relation between free energy and entropy? vS , 0

porte
完美品格 GSponteneous
S = 0 ok
() 焓
,

• What is the relation between free energy and enthalpy?

3
Entropy 熵
Solids are more ordered than liquids or
gases and thus have lower entropy.

• What is entropy (S)? 㣕

视為可選进擇撑可位置的就 diumond )
→

Cagraphitl
⼼選擇多
-
3 ⼤ ,

選少⼩
gas solid

• Why does entropy be viewed as a measure of

molecular randomness or disorder?

s ⼒學
• Entropy is a thermodynamic function that
describes the number of arrangements
(positions and/or energy levels) that are
available to a system existing in a given state.

• Entropy is closely associated with probability.

4
 0
∞ 低壓

糖⽔ → 糖⽔,
"

《 …
⻅

— ) → Iacs )
⼀
— bag
s 1
bz
4S
-
±

比 . 2
Sd
5

b .
abi 0
 第⼀ 能量守 恆 :
,

spoforreous ⾃發
即

a Saorio 20

The second law of thermodynamics

曰

䚨
• In any spontaneous process there is always an increase in the
entropy of the universe (∆𝑆 ).
⼀

totalso
S 上

Suniv aSsurr
4 = 4
Sbys t

• ∆𝑆 and ∆𝑆 represent the changes in entropy that occur in

the system and surroundings, respectively.

6
 Hroa
修 sys
⼀
2 O
4

What happens to the entropy of H2O(l)  H2O(g)?

时 ~

• A mole of water has a volume of approximately 18 mL. A mole of

steam at 1 atm and 100℃ occupies a volume of approximately 31 L.
• The vaporization of water is favored by this increase in positional
probability. ∆𝑆 has a positive sign.

• What about the entropy change in the surroundings?

放熱
• An exothermic process transfers heat to the surroundings. This flow
of energy increases the random motions of atoms there and
increases the entropy of the surroundings. The sign of ∆𝑆 >0
呢熱
• An endothermic process transfers heat from the surroundings. This
flow of energy decreases the random motions of atoms there and
decreases the entropy of the surroundings. The sign of ∆𝑆 <0
4 Ssuri =

=
assurr
等 7
 冶⾦ 銻

礦 ⽤鐵 還原
a 。

_
H
4 Ssarr
=
T
125 KJ
a .

dSarr = —

298 K
:

8
Free Energy
• ∆𝑆 ∆𝑆 ∆𝑆 必固定下

|
at = - IS
.
ree
U

constant temp
H
A

asar =

⼀
H 4

aSaniv =
aSsys +
于

• 𝑇 ∆𝑆 𝑇 ∆𝑆 Δ𝐻
• 𝑇 ∆𝑆 ∆𝐺 Δ𝐻 𝑇 ∆𝑆
LGCO =
spontaneous
• A process (at constant T and P) is spontaneous in the direction
in which the free energy decreases (- ∆ G= T∆𝑆

9
Is it spontaneous?
• H2O(S)  H2O(l)

0
sys syS

20

30 7
=
spontaneous

aG H Tas
T Sanio 4
-

= =
-
在

10
 hroo /mol

'
— poneasonsiiasI
G = 4 H -
Tas
4

z 100 O - T ×9 } <

⼠3 333 S

3
nken I 333 k
2 ,
- GcO Ʃ
EPortUdeods

11
 ⼀

298 k

aSsog s 0uyy- aslory ) =

-
187
4S = S
)2
{

4 H
0
=
2 aHfisonigi) - 24 Htsoig " -
aHtcoryy
= - 198K

H - tuso
0

4 G = 4

= -

198 -
298 x 6
-
18 n) xoo

12
ld (s ) +
θ
→ lOug)
g ' 4 G 是 -
39 YKJ
4 G 394 K
Cory 1 → s
Cg
)
tOrg ) =

Cdcs ) 0 3K
Cys eG
→
) =
-

13
 GH 3 OHil ) ⾥醇豪

izig EH3 OH]

COogl )
→
t

甲醇京 辫

)
G 。 4 { 229) - 394)
×
-
6 163
+ 2×
-
2×
-

最定態
foruatiod reaolioM

IHrtaig "

Oag
)
→
koce !

最稳定態熱 4 ff

aH 品 ?
CH 4 cg) +θ= cy ) →
COrcyltHrOcl :

tuguttatet
Gusstiig
. '

1
COrig
别 OrCf → )affcont
正烯 edevgy shange
Gesit
forreafion reddion
(
free 1

ittr o

「
HicyitzOsgi fHiocy → . t

Htsl
(molaaill
ffumariunrartionanthufytmone
wuilm
號
× d/ G 是 - Mo1
-123) - 60 co

] + 1 ×③ -

{ x ) = aHpin
zx

Gzt4 cg ) 52
的 219 14
2 HrO
zHztO 2
-
→

HzOcl ) 286 ⼀ 3
到 “ Or → {☆王
-
息 +

GH 4 → C+ 2 H 2

[ zrl 5 θ Hcl] 27
- 5
M 海
the free energy of an ideal gas depend on its pressure

• 𝐺 is the free energy of the gas at a pressure of 1 atm,

• 𝐺 is the free energy of the gas at a pressure of P atm,
• R is the universal gas constant, and
• T is the Kelvin temperature.

15
16
Equilibrium =0

17
18
The Temperature Dependence of K

19
The maximum possible useful work
• The maximum possible useful work obtainable from a process
at constant temperature and pressure is equal to the change in
free energy:

• ∆𝐺 𝑊

20
LAW OF MASS ACTION
• N2(g) + 3H2(g)  2NH3(g)

• Use LAW OF MASS ACTION to express K.

• What is its Standard reaction enthalpy?

• What is its Standard free energy?

• After equilibrium, if heating the reaction system again, which

direction will the reaction shift toward?
21
Theoretical electrical energy
• 2H2(g) + O2(g)  2H2O (g)

• What is its Standard reaction enthalpy?

• What is its Standard free energy?

• How much electrical energy will the above reaction produce at

most via a fuel-cell equipment?

22
Thermodynamic laws
• 0th law
• If two systems are each in thermal equilibrium with a third system, then
they are in thermal equilibrium with each other.
• 1st law
• The law of conservation of energy

• 2nd law
• In any spontaneous process there is always an increase in the entropy of
the universe (∆𝑆 ).

• 3rd law
• the entropy of a perfect crystal at a temperature of zero Kelvin (absolute
zero) is equal to zero.
23
The end of Ch17

24