Chemical Thermodynamics
Chemical Thermodynamics
Chemical Thermodynamics
THERMODYN
AMICS
OBJECTIVES
Processes that
are spontaneous
in one direction
are
nonspontaneous
in the reverse
direction.
Processes that are spontaneous at one temperature may be
nonspontaneous at other temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.
Spontaneous @ T
< 0ºC
Is the
spontaneity of
melting ice
dependent on
anything?
Spontaneous @ T
> 0ºC
SPONTANEOUS VS
NONSPONTANEOUS
ENTROPY
Equilibrium process:
Suniverse = Ssystem + Ssurroundings = 0
ENTROPY CHANGES IN THE
SYSTEM
S = -89.6
THERMODYNAMIC CHANGES IN
☺
SYSTEMS (CHEM. REACTIONS)
Hsys
Ssurr
T
If the entropy change for a system is known
to be 187.5 J/Kmol and the enthalpy
change for a system is known to be 35.8
kJ/mol, is the reaction spontaneous?
Spontaneous if: Suniv= Ssys + Ssurr > 0
Hsys
Ssurr
T
Is the reaction spontaneous?
35,800 J/mol
Ssys 120.0J/K mol
298 K
G = H – T S
ΔH (KJ/mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
(-484.5) (-393.5) (-241.8)
ΔS (J/K mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
159.8 205.1 213.7 188.8
Calculate ΔG at 25°C for the following reaction,
will this reaction be spontaneous at this
temperature?
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
ΔG (KJ/mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
-389.9 (-394.4) (-228.6)
PREDICTING TEMPERATURE
FROM GIBBS EQUATION
H 125 kJ/mol
T 385 K
S 0.325 kJ/K×mol
385 K 273 = 112C
FREE ENERGY AND
CHEMICAL EQUILIBRIUM
Reactions are almost always in
something other than their standard
states.
Free energy is needed to determine if a
reaction is spontaneous or not.
How does free energy change with
changes in concentration?
FREE ENERGY AND
EQUILIBRIUM
G = G° + RT ln Q
G = non-standard free energy
G° = standard free energy (from
tables)
R = 8.314 J/K·mole
T = temp in K
Q = reaction quotient
Consider the reaction,
H2(g) + Cl2(g) 2 HCl(g)
How does the value of G change when the
pressures of the gases are altered as follows at 25
C?
H2 = 0.25 atm; Cl2 = 0.45 atm; HCl = 0.30 atm
Gfo (KJ/mol)
H2(g) + Cl2(g) 2 HCl(g)
0 0 (-95.27)
FREE ENERGY AND
EQUILIBRIUM
First, calculate standard free energy:
H2(g) + Cl2(g) 2 HCl(g)
G° = [2(95.27 kJ/mol)] [0 + 0] =
190.54 kJ/mol
Second, find Q:
(P )2 (0.30) 2
QP HCl 0.80
(P ) (P ) (0.25) (0.45)
H Cl
2 2
FREE ENERGY AND
EQUILIBRIUM
Solve: G = G° + RT ln Q
G = 190,540 J/mol + (8.314J/K·mol)(298 K)
ln (0.80)
At equilibrium, G = 0 and Q = K
The equation becomes:
0 = G° + RT ln K
or
G° = – RT ln K
K=e -G°/RT
RELATIONSHIP BETWEEN G°
AND K
RELATIONSHIP BETWEEN G°
AND K
NO2(g) N2O4(g)
ΔGfo (KJ/mol) 51.31 97.89
PRACTICE