GENERAL CHEMISTRY 2

2ND LAW OF
THERMODYNAMICS
It was developed in the middle of the 19th
century by German physicist Rudolf
Clausius and Scottish physicist William
Thomson, also know as Lord Kevin
 The second law of thermodynamics is a
core principle in physics and engineering
that deals with the concept of entropy and
the direction of natural processes. It states
that when energy is formed or transferred,
more and more of it was wasted.
According to this principle, the entropy of
any closed system tends to increase or
remain constant but never decreases. It is
typically used to predict the energy
exchanges that occur in the following
processes: chemical reactions.
ENTROPY
 Entropy is defined as the randomness or disorder.
Disorder refers to the direction of the location of
moleculles or energy.
In thermodynamics, entropy is a measure of the
amount of energy in a system that is unavailable to
do work. The higher the entropy, the more
disordered or random the system is. Meanwhile, the
lower the entropy, the more organized and
predictable the system is.
COMPUTING THE
STANDARD
ENTROPY OF A
REACTION
Supposing a system is represented by the
reaction below:
aA + bB → cC + dD
 EXAMPLE

aA + bB →
cC + dD
⇌
N2(g)+3H2(g) 2NH3(g)

wherein the small letters indicate the coefficient

of each compound and the capital letters indicate
the actual compounds
The difference between the standard entropies
of the products and the re-
actants is the standard entropy of the reaction
(ΔS°r).
 ΔS°r = ΣnS°(products) - ΣmS°(reactants)
or
Standard entropy of a reaction =
standard entropy of products - standard
entropy of reactants
where n and m are the stoichiometric
coefficients in the reaction.
 ΔS°r = ΣnS°(products) - ΣmS°
(reactants)
or
Standard entropy of a reaction =
standard entropy of products -
standard entropy of reactants
 In details, ΔS°r
of the above for the previous reaction
is expounded to
ΔS°r = [cS°(C)+ dS°(D)] - [aS°(A) + bS°
(B)]
 The standard entropy values of
compounds are measured in J/K -
mol. A thermodynamic table lists the
absolute entropy of substances at
25°C and 1 atm.
GIBB'S FREE
ENERGY
 It was developed by Josiah Wiiliard
Gibbs in the 1870’s. Gibb’s free energy
was defined as the available energy in
a system.
It is the maximum amount of energy
present in a thermodynamic system
that can be used to perform at a
constant temperature and pressure.
 Gibbs free energy can be used to
determine if a reaction will be
spontaneous, nonspontaneous, or at
equilibrium.
Negative value = spontaneous
Positive value = nonspontaneous
 ΔG= ΔH-TΔS
Where:
G is the free energy
H is the enthalpy
T is the temperature
S is entropy
APPLICATION
 Refrigerators:
According to the Second Law of
Thermodynamics, heat always flow
spontaneously from hot to cold naturally.
However, refrigerator add work in order for
heat to flow from cold to hot cooling the space
inside the of it that prolong the shelf life of
foods.
 Engines:
The second law of thermodynamics indicates
that heat cannot be completely converted into
work. It means that there will always be losses
that limits the efficiency of engines. Using
second law of thermodynamics, the efficiency of
engines can be maximized by operating an
engine between two given temperatures.
PRACTICE
PROBLEMS
 ΔH° ΔG° S°
(kJ/mol) (kJ/mol) (J/mol)

Hg (1) 0 0 76.0

Hg (g) 61.3 31.8 174.9

HgO (s) -90.8 -58.5 70.3

02 (g) 0 0 205.0
 2 HgO (s) → 2 Hg (l) + O2 (g)
a. Determine ΔH° at 298 K
b. Determine S° for the system at 298 K
c. Determine S° for the universe at 298 K
d. Determine ΔG° at 298 K
e. Are the results in part c and d consistent? Explain
using spontaneity
ΔH ΔS Low Temperature High Temperature

Spontaneous Spontaneous
- +
ΔG < 0 ΔG < 0

Nonspontaneous Nonspontaneous ΔG
+ -
ΔG > 0 >0

Spontaneous Nonspontaneous ΔG
- -
ΔG < 0 >0

Nonspontaneous Spontaneous
+ +
ΔG > 0 ΔG < 0
f. To determine if the following reaction will occur
spontaneously at 25 C, use the values of H and S to
determine it.
 Answers

a. ΔH°289k = nΣΔH°f(products) - nΣΔH°f(reactants)

2 HgO (s) → 2 Hg (l) + O2 (g)
ΔH°289k = [ 2(Hg) + O2] - [ 2 (HgO) ]
= [ 2(0) + 0 ] - [ 2 (-90.8) ]
ΔH°289k = 182 kJ/mol
b. ΔS° = ΣnS°289(products) - ΣnS°289(reactants)
2 HgO (s) → 2 Hg (l) + O2 (g)
ΔS°sys = [ 2(Hg) + O2] - [ 2 (HgO) ]
= [ 2(76.0) +205.0] - [ 2 (70.3) ]
ΔS°sys = 216 J/mol K
c. ΔSuniv = ΔSsys - ΔH/T

Gevin:
ΔH°289k = 182 kJ/mol convert to J → 182000 J/mol
ΔS°sys = 216 J/mol K
T = 298 K
ΔSuniv = ΔSsys + ΔSsurr
ΔSsurr = - ΔH/T

ΔSuniv = ΔSsys - ΔH/T

= 216 J/mol K - 182000 J/mol
ΔSuniv = -394 J/mol K
d. ΔG° = ΣnG°289 (products) - ΣnG°298(reactants)
2 HgO (s) → 2 Hg (l) + O2 (g)
ΔG°289 = [ 2(Hg) + O2] - [ 2 (HgO) ]
= [ 2(0) + 0] - [ 2 (-58.5 ]
ΔG°298 = 117 kJ/mol
ΔSuniv = -394 J/mol K ΔG°298 = 117 kJ/mol
Yes, since the ΔS is negative while ΔG is
greater than 0, in the table it will be both
nonspontaneous.
f. TK = 25o C + 273.15 = 298.15 K
Go = Ho - T So
H = -92.22 kJ (favorable)
S = -198.75 J/K (unfavorable)
= -92,220 J - (298.15 K x -198.75 J/K)
= -92,220 J + 59,260 J
= -32,960 J
= 32.96 kJ
THANK YOU FOR LISTENING!

Alfahad Jhovan Ibrahim Ma. Eloisa Presto

Angelica Jean Malbas Marianne Rein Petelo
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