CHEMICAL

THERMODYN
AMICS
• C:\Users\DEPED\Desktop\ENTROPY AND SPONTAN
EOUS PROCESSES.mp4
Spontaneous Processes
• Spontaneous: process that does occur
under a specific set of conditions
• Nonspontaneous: process that does not
occur under a specific set of conditions
Spontaneous Processes
• Often spontaneous processes are exothermic,
but not always….
• Methane gas burns spontaneously and is
exothermic
• Ice melts spontaneously but this is an
endothermic process…
• There is another quantity!
Spontaneous Processes
• can proceed without any outside intervention.
Processes that {Spontaneity}
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 0C it is spontaneous for ice to melt.
• Below 0C the reverse process is spontaneous.

Spontaneous @ T
< 0ºC
Is the
spontaneity of
melting ice
dependent on
anything?
Spontaneous @ T
> 0ºC
Spontaneous vs Nonspontaneous
Entropy
• Entropy (S): Can be thought of as a measure
of the disorder of a system

• In general, greater disorder means greater

entropy
Standard Entropy
• Standard entropy: absolute entropy of a substance at
1 atm (typically at 25C)
What do you notice about entropy values for
elements and compounds?
• Units: J/K·mol
Entropies
Trends in Entropy
• Entropy for gas phase is greater than that of liquid
or solid of same substance
• I2 (g) has greater entropy than I2 (s)
• More complex structures have greater entropy
• C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower entropy
• Diamond has lower entropy than graphite
Entropy Changes in a System
Qualitative
• Ssolid < Sliquid
Entropy Changes in a System
Qualitative
• Sliquid < Svapor
Entropy Changes in a System
Qualitative
• Spure < Saqueous
Entropy Changes in a System
Qualitative
Slower temp < Shigher temp
Entropy Changes in a System
Qualitative
• Sfewer moles < Smore moles
Standard Entropies
• Standard entropies tend to increase with increasing molar
mass.

• Larger and more complex molecules have greater entropies

(greater ways to execute molecular motions)

{*Entropy&MolecuarSize} {Entropy&Temp}C7H15 @ 500 K S=921J/nK vs, @ 200 K

Entropy Changes in a System
Qualitative
Determine the sign of S for the following
(qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a
solid yellow precipitate forms
3. Liquid water is heated from 22.5 C to
55.8 C
 Concept Check

Predict the sign of S for each of the

following, and explain:
a) The evaporation of alcohol
b) The freezing of water
c) Compressing an ideal gas at constant
temperature
d) Heating an ideal gas at constant pressure
e) Dissolving NaCl in water
REVIEW
• Predict whether the entropy change of the system in
each of the following is positive or negative.
• N2 (g, 10 atm) —> N2 (g, 1atm).
• 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g).
• 2 H2 (g) + O2 (g) —> 2 H2O (l)
• NH4Cl (s) —> NH3(g) + HCl (g)
The Second and Third Laws of
Thermodynamics
• System: the reaction
• Surroundings: everything else

• Both undergo changes in entropy during

physical and chemical processes
Second Law of Thermodynamics
• Entropy of the universe increases in a
spontaneous process and remains unchanged
in an equilibrium process.

• Equilibrium process: caused to occur by

adding or removing energy from a system
that is at equilibrium
Second Law of Thermodynamics
• Mathematically speaking:
Spontaneous process:
Suniverse = Ssystem + Ssurroundings > 0

Equilibrium process:
Suniverse = Ssystem + Ssurroundings = 0
Entropy Changes in the System

Entropy can be calculated from the table of

standard values just as enthalpy change was
calculated.

Srxn = nS products  mS reactants

Standard Entropy
• Calculate the standard entropy change for the
following using the table of standard values.
(first, predict the sign for S qualitatively)
• SN2 = 191.5 J/mole K;
• SH2 = 131 J/mole K;
• SNH3 = 193 J/mole K
2NH3(g)  N2(g) + 3H2(g)
 2NH3(g)  N2(g) + 3H2(g)

Srxn = nS products  mS reactants

= [(1)(191.5 J/K · mol) + (3)(131.0 J/K · mol)]

- [(2)(193.0 J/K · mol)]
= 584.5 J/K · mol - 386 J/K · mol
Srxn = 198.5 J/K · mol (Entropy increases)
(2 mol gas  4 mol gas)
• Calculate the standard entropy change for
the following using the table of standard
values.
• SH2O = 188.7 J/mole K;
• SH2 = 131 J/mole K;
• SO2 = 205 J/mole K
2H2(g) + O2(g)  2H2O (g)

S = -89.6
Thermodynamic Changes in Systems
(Chem. Reactions)
☺
Hrxn =  Hf (products) - Hf (reactants)
So298   Soproducts   Soreactants

Grxn =  Gf (products)   Gf (reactants)

Entropy Changes in the Surroundings
• Change in entropy of surroundings is directly
proportional to the enthalpy of the system.
Ssurroundings   Hsystem

Notice: exothermic process corresponds to

positive entropy change in surroundings
Entropy Changes in the Surroundings
• Change in entropy of surroundings is
inversely proportional to temperature
Ssurroundings  1 / T

Combining the two expressions:

Hsys
Ssurr 
T
If the entropy change for a system is known to
be 187.5 J/Kmol 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

Suniv= -187.5 + 120.0 < 0 so the reaction is

non-spontaneous
Problem: Calculate the Suniv for the synthesis of
o
ammonia @ 25 C.
N2 (g) + 3 H2 (g)  2 NH3 (g)

H°rxn = - 92.6 kJ/mol

• SN2 = 191.5 J/mole K;

• SH2 = 131 J/mole K;
• SNH3 = 193 J/mole K
Entropy Change in the Universe
Suniv = Ssyst or rxn + Ssurr
nS(prod) - mS(react)
-Hsys
Ssurr =
T
2(192.5) – [(191.5)+3(130.6)]
 (92.6 kJ / mol x 1000 J / kJ)

298 K
S°syst = - 199 J/K·mol
Ssurr = 311 J/K·mol

Suniv = - 198.3 J/K·mol + 311 J/K·mol

Suniv = 113 J/K·mol
• 3. Is the reaction spontaneous at 25 C?
• N2 (g) + 3 H2 (g) —> 2 NH3 (g) ΔH°rxn = - 92.6
kJ/mol

• N2 (g) + 3 H2 (g) —> 2 NH3 (g)

• From the table, S°(J/K· mol):
• 192 131 193
Third Law of Thermodynamics
• “The entropy of a perfect crystalline substance is
zero at the absolute zero of temperature.”
• At absolute zero (T = 0 K= -273.15 oC), the entropy
of a perfect crystal is 0.
• As the temperature increases, the freedom of motion
increases. The entropy of any substance at a
temperature above 0 K is greater than zero.
• 1. Determine ΔS for the reaction:
• SO3(g) + H2O(l) —> H2SO4(l)
• Given: S°(J/K·mol):
• 256.2 69.9 156.9
• 2. Calculate ΔS for the reaction
• SO2(s) + NO2(g) —> SO3(g) + NO(g)
• Given: S°(J/K·mol):
• 248.5 240.5 256.2 210.6
3. Calculate ∆S° for the following reaction:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)

Given the following information:

S° (J/K·mol)
Na(s) 51
H2O(l) 70
NaOH(aq) 50
H2(g) 131
Standard Free Energy Changes

Free energy can be calculated from the table

of standard values just as enthalpy and
entropy changes.

Grxn = nG products  mG reactants

Standard Free Energy Changes

Calculate the standard free-energy change for the

following reaction.
2KClO3(s)  2KCl(s) + 3O2(g)
GKCl = 408.3 kJ/mol;
GO2 = 0
GKClO3 = 289.9 kJ/mol
Grxn = nG products  mG reactants
= [2(408.3 kJ/mol) + 3(0)]  [2(289.9 kJ/mol)]
= 816.6  (579.8) = 236.8 kJ/mol (spont)
• Find the standard Gibbs energy change for the
reaction
• CaCO3(s) → CaO(s)+ CO2(g)
• The ΔGf° values for the three components of this
reaction system are
• CaCO3(s): –1128 kJ/ mol
• CaO(s): –603.5 kJ/mol
• CO2(g): –137.2 kJ/mol
 EVALUATION
2 C6H6 (l) + 15 O2 (g) 12 CO2(g) + 6 H2O(g)

Calculate the standard free energy changes for the above

reaction @ 25 °C.
Standard Molar
Gibbs Energy of
Formation (Gf)
CO2 (g) -394
H2O (g) -229
C6H6 (l) 125
Gibbs Free Energy
G = H – T S

• The Gibbs free energy, expressed in terms of

enthalpy and entropy, refers only to the
system, yet can be used to predict
spontaneity.
Gibbs Free Energy
• If G < 0,negative, the forward reaction is
spontaneous.
• If G = 0, the reaction is at equilibrium.
• If G > 0, positive, the forward reaction is
nonspontaneous
EXAMPLE
• Determine if this reaction is spontaneous
under standard conditions; knowing that the
reaction's change
in enthalpy is ΔH∘=−144 kJ, and its change
in entropy is ΔS∘=−36.8 J/K.
• 4KClO3(s)→3KClO4(s)+KCl(s)
EXAMPLE
• What is the standard free energy change ΔG for the
following reaction at 25oC?
• N2 + 3H2 → 2NH3
• ΔHfo (KJ/mol) So (J/K mol) ΔGfo (KJ/mol)
• N2 191.610
• H2 130.684
• NH3 -46.11 192.450 -16.45
• 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)
• 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
• Set G = 0 (equilibrium condition)
0 = H – T S

Rearrange equation to solve for T- watch for

units!
This equation will also be useful to calculate
temperature of a phase change.
Example
For a reaction in which H = 125 kJ/mol and S =
325 J/Kmol, determine the temperature in Celsius
above which the reaction is spontaneous.

H 125 kJ/mol
T    385 K
S 0.325 kJ/K×mol
385 K  273 = 112C
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)

G =  191.09 kJ/mol (the reaction becomes more

spontaneous - free energy is more negative)
• Consider the reaction,
O2(g) + 2CO(g)  2CO2(g)
How does the value of G change when the
pressures of the gases are altered as follows at 25
C?
• O2 = 0.50 atm; CO = 0.30 atm;
CO2 = 0.45 atm
ΔGfo
O2(g) + 2CO(g)  2CO2(g)
0 -137.168 -394.359
Relationship Between G° and K

• 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

• Using the table of standard free energies, calculate

the equilibrium constant, KP, for the following
reaction at 25 C.
2HCl(g) H2(g) + Cl2(g)
G° 95.27 kJ/mol 0 0
 Relationship Between G° and K

First, calculate the G°:

= [0 + 0]  [2(95.27 kJ/mol)]
= 190.54 kJ/mol (non-spontaneous)
Substitute into equation:
190.54 kJ/mol =  (8.314 x 103 kJ/K·mol)(298 K) ln KP
76.90 = ln KP = 3.98 x 1034
K < 1 reactants are favored
• Calculate the value of the equilibrium constant, KP,
for the following reaction at 25 C.
2NO2(g) N2O4(g)

NO2(g) N2O4(g)
ΔGfo (KJ/mol) 51.31 97.89
 PRACTICE
• 1. Calculate the entropy change for the following reactions:
• A. C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g)
• S° 270.3 205.0 213.6 188.7 J/K mol
• B. CO(g) + 2H2(g)  CH3OH(g)
• S° 197.9 131.0 239.9 J/K mol
• 2. Calculate the Gibbs Free Energy for the following
reactions:
• A. N2(g) + 3H2(g)  2NH3(g) at 25 oC
∆Ho = -92 kJ and ∆ So = -199 J/K = -0.199 kJ/K
B. CH4(g) + H2O(g)  CO(g) + 3H2(g) at 25 oC
∆ Ho = 206 kJ and ∆ So = 216 J/K = 0.216 kJ/K
• 3. The old camera flash bulb used Mg metal sealed in a
bulb with oxygen. The reaction is:
• Mg + ½ O2 —> MgO
• S° J/K mol: 32.7 205.0 26.9
• ΔHfo kJ/mol: 0 0 -601.2
• 4. At what temp will a reaction occur? Given the
following reaction and data:
• N2(g) + O2 (g) —> 2 NO (g)
• Δ S J/K mol: 192 205.0 211
• ΔHfo kJ/mol: 0 0 90
• 5. Find the value for the equilibrium constant, K,
at 25 °C (298 K) for the following reaction. The
standard free energy change, ΔG°, at 25 °C equals
–13.6 kJ.
• 2NH3 (g) + CO2 (g) → NH2CONH2 (aq) + H2O(l)