Entropy
For any spontaneous process, total entropy change
(DST)
must be positive:
DST
> 0 SPONTANEOUS
DST
<
0 NOT SPONTANEOUS
DST
= 0 EQUILIBRIUM
Free Energy
DST
= DSSYS
+ DSSUR
DSSUR
= -DHSYS/T
DST
= DSSYS
- DHSYS/T
(multiply
this equation by -T)
-TDST
= -TDSSYS
+ DHSYS
Define DG as -TDST(DG
called Gibbs free energy)
DG = DH
- TDS (since
only using SYS subscript, omit SYS/SUR subscripts)
DG
< 0 SPONTANEOUS
DG
> 0 NOT SPONTANEOUS
DG
= 0 EQUILIBRIUM
Explain:H2O(s)
H2O(l)(spontaneous
at 20°C)
Solid
Liquid
DS positive
(favorable)
Gains Heat DH
positive (unfavorable)
spontaneous only if
TDS
>
DH
TDS
= DH
at 0°C (equilibrium)
ice melts above 0°C
Explain:
H2O(l)
H2O(s)(spontaneous
at -10°C)
Liquid
Solid
DS
negative (unfavorable)
loses Heat DH
negative (favorable)
spontaneous only if
DH
>
TDS
TDS
= DH
at 0°C (equilibrium)
water freezes below 0°C
Calculate
temperature
range when reaction can be spontaneous:
N2
+ 3H2
2NH3
DH
= 2DH(NH3)=
2(-46kJ) = -92kJ
DS
= S2 -
S1 = 2S(NH3) - 3S(H2)-
S(N2) =
2(192 J/K) - 3(131 J/K) -
192 J/K = -200 J/K
T =
DH/DS
= -92000J/(-200J/K)
= 460K = 187°C
SPONTANEOUS
FOR T<187°C
