Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Exercises (True or False)

Chemical Thermodynamics: 1. Enthalpy is an intensive property.
Heat and Thermochemistry 2. The 2nd law of thermodynamics states that
the entropy of a pure crystalline solid at 0 K
is zero.
3. In ∆H measurements, standard conditions
are defined as 25.0 °C and 1.00 atm .
4. Condensation is a process accompanied by
an increase in ∆S.
5. A positive (+) heat (q) value for a system
indicates that energy is absorbed by the
system.

Exercises (Problem Solving) Exercises (Problem Solving)

1. In burning of gasoline in a car engine, 2. Given the following thermochemical

the system releases 325 J of heat to the equation, how much heat (in kJ) evolves
surroundings. The expanding gases also when 10.0 g of H2 reacts with 5.00 g of
do 451 J of work to push the pistons Cl2 to form the acid?
outward. Calculate the change in energy
of the system (in cal). H2(g) + Cl2(g)
2 HCl(g) ∆H = -185 kJ/mol

Exercises (Problem Solving) Fundamental Laws

3. Determine the ∆H°for the reaction which 2nd Law of Thermodynamics

occurs in a welder’s acetylene torch.
2 C2H2(g) + 5 O2(g)
4 CO2(g) + 2 H2O(l) “In spontaneous changes, the
universe tends towards a state of
Use the following thermochemical equations: greater disorder.”
H2(g) + ½ O2(g)
H2O(l) ∆H = -285.8 kJ/mol
2 C(s) + H2(g)
C2H2(g) ∆H = +226.7 kJ/mol
C(s) + O2(g)
CO2(g) ∆H = -393.5 kJ/mol
Spontaneity of Physical and
Chemical Changes
• Spontaneous changes happen without any
continuing outside influences.
• A spontaneous change has a natural direction.
• Example: rusting of iron & melting of ice at room
temperature occurs spontaneously.
Entropy, S
• Entropy is a measure of the disorder or
randomness of a system.
• Also a state function and follow the
following sign conventions:
– ∆S > 0 disorder increases
(which generally favors spontaneity).
– ∆S < 0 disorder decreases
(generally does not favor spontaneity).
Entropy, S
Aspects of Spontaneity
1. An exothermic reaction (∆H) does not
ensure spontaneity.
– For example, the freezing of water is
exothermic but spontaneous only below 0oC.
2. An increase in disorder (∆S) of the system
also does not insure spontaneity.
A proper combination of exothermicity and
disorder that determines spontaneity. (∆G)
Entropy, S
• From the Second Law of Thermodynamics, one
condition for a spontaneous process to occur:
∆Suniverse = ∆Ssystem + ∆Ssurroundings > 0
• In general for a substance in its three states of
matter:
Sgas > Sliquid > Ssolid
Entropy & the 3rd of
Thermodynamics
• The 3rd Law of Thermodynamics
states, “The entropy of a pure,
perfect, crystalline solid at 0 K is
zero.”
• This law permits us to measure the
absolute values of the entropy for
substances.
Entropy, S Entropy, S
• Entropy changes for reactions can be • Example: Calculate the entropy change for the
determined similarly to ∆H for reactions. following reaction at 25oC.
2 NO →N O
←
2(g) 2 4(g)

∆S o
298 = ∑ nS o
products − ∑ nS o
reactants ∆Srxn
o
= ∑n o
Sproducts − ∑n S o
reactants
n n n n

= SNo 2O4(g) − o
2SNO2(g)

= (304.2 J
mol K) − 2(240.0 J
mol K)
= −175.8 J
mol K or - 0.1758 kJ
mol K

Entropy, S Entropy, S
• Calculate the ∆S°for the reaction:
• The negative sign of ∆S indicates that
O2(g) + 2 H2(g)
2 H2O(g)
the system is more ordered.
• If the reaction is reversed the sign of
∆S changes. Given:
• For the reverse reaction O2(g) S°= 205.0 J/mol-K
∆So298= +0.1758 kJ/K H2(g) S°= 130.6 J/mol-K
• The (+) sign indicates the system is
more disordered. H2O(g) S°= 188.7 J/mol-K

More On The 2nd Law of Free Energy Change, ∆G

Thermodynamics
• “In spontaneous changes the universe tends
towards a state of greater disorder.”
• Spontaneous processes require:
1. The free energy change of the system must be
a negative quantity.
2. The entropy of universe must increase, i.e.
fundamentally, the system must be capable of
doing useful work on surroundings for a
spontaneous process to occur.
• In the mid 1800’s J. Willard
Gibbs determined the
relationship of enthalpy, H, and
entropy, S, that best describes
the maximum useful energy
obtainable in the form of work
from a process at constant
temperature and pressure.
• The relationship also describes
the spontaneity of a system.
Free Energy Change, ∆G Free Energy Change, ∆G

• Example: Calculate ∆Go for the reaction.

• Changes in free energy obey the same type
of relationship we have described for
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
enthalpy, ∆H, and entropy, ∆S, changes.
∆Grxn
o
= [3∆Gof CO2(g) + 4∆GfoH2O(l ) ] − [∆Gof C3H8(g) + 5∆Gof O2(g) ]
= {[3(−394.4) + 4(−237.3)] − [(−23.49) + 5(0)]} kJ mol
∆G 0298 = ∑ n∆G 0products − ∑ n∆G 0reactants = −2108.9 kJ mol
n n

Free Energy Change, ∆G Free Energy Change, ∆G

• Calculate the ∆G°for the reaction:
6 H2O(l) + 6 CO2(g)
2 C6H12O6(s) + 6 O2(g) • The relationship of the new state
function, ∆G, the Gibbs Free Energy
Given: with enthalpy, ∆H, and entropy, ∆S.
C6H12O6(s) ∆G°= -916.0 kJ/mol
CO2(g) ∆G°= -394.4 kJ/mol ∆G = ∆H - T∆S (at constant T & P)
H2O(l) ∆G°= -237.2 kJ/mol
O2(g) ∆G°= 0.000 kJ/mol

Free Energy Change, ∆G,

Free Energy Change, ∆G
and Spontaneity
• Example: Calculate ∆So for the following reaction.
Note: ∆Ho= -2219.9 kJ, and ∆Go= -2108.5 kJ. • The change in the Gibbs Free Energy, ∆G, is
CH +5O → 3 CO + 4 H O
a reliable indicator of spontaneity of a
3 8(g) 2(g) 2(g) 2 (l)
physical process or chemical reaction.
∆G = ∆H − T∆S
o o o

• However, ∆G does not tell us how quickly the

∆H − ∆G = T∆S
o o o
process occurs.
∆H − ∆G o o

= ∆S o

T • ∆G > 0 reaction is non-spontaneous

[− 2219.9 − (− 2108.5)] kJ
∆S o
=
298 K
• ∆G = 0 system is at equilibrium
∆S = −0.374
o kJ = -374 J • ∆G < 0 reaction is spontaneous
K K
Free Energy Change, ∆G, Free Energy Change, ∆G,
and Spontaneity and Equilibrium
 ∆Go < 0, so the reaction is spontaneous • Example: Use thermodynamic data to
at standard state conditions. estimate the normal boiling point of water.

→H O
H 2O (l) ← 2 (g)
 If the reaction is reversed: Because this is an equlibrium process ∆ G = 0.
∆Go > 0, and the reaction is ∆H
Thus ∆ H = T ∆ S and T =
nonspontaneous at standard state ∆S
conditions.

Free Energy Change, ∆G, Free Energy Change, ∆G,

and Equilibrium and Equilibrium
assume ∆ H@ BP ≈ ∆ H o298 assume ∆S @ BP ≈ ∆S0rxn • Estimate the boiling point of PCl3.
∆ H o = ∆ H oH 2 O (g) − ∆ H oH 2 O ( l ) ∆S0rxn = S0H 2 O( g ) − SH0 2 O( l )
∆ H o = [ − 241.8 − ( − 285.8 ) ] J K ∆S0rxn = [188.7 − 69.91] J K ∆Hf° ∆Sf°
∆ H = + 44 .0 kJ@25 C
o o
∆S0rxn = 118.8 J K or 0.1188 kJ K
Liquid PCl3 -319.7 kJ/mol 217.1 J/mol-K

∆H ∆Ho 44.0 kJ Gaseous PCl3 -287.0 kJ/mol 311.7 J/mol-K

T = ≈ = = 370 K
∆S ∆So 0.1188 kJ K
370 K - 273 K = 97o C

The Temperature
“remember, when the world
Dependence of Spontaneity pushes you to your knees,
• Free energy has the relationship ∆G = ∆H -T∆S. you’
you’re in the perfect position
• Because 0 ≤ ∆H ≥ 0 and 0 ≤ ∆S ≥ 0, there are four to pray”
pray”
possibilities for ∆G.
∆H ∆S ∆G Forward reaction spontaneity
<0 >0 <0 Spontaneous at all T’s
<0 < 0 T dependent Spontaneous at low T’s questions?
>0 > 0 T dependent Spontaneous at high T’s
>0 <0 >0 Nonspontaneous at all T’s
Announcement

Chem 16 Lecture
1st Long Exam

16 August 2010
8:00-10:00