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DG 1

1. Chlorine trifluoride is a toxic, intensely reactive gas. It


was used in World War II to make incendiary bombs. It
reacts with ammonia and forms nitrogen, chlorine, and
hydrogen fluoride gases. When two moles of chlorine
trifluoride reacts, 1196 kJ of heat is evolved.
Write the thermochemical equations for the reaction
What is the H
o
f
for ClF
3
?

2. Consider the combustion of one mole of acetylene, C
2
H
2
,
which yields carbon dioxide and liquid water. Using the given
below,
Hf (kJ/mol): C
2
H
2(g)
= +226.7, CO
2(g)
= -393.5,
H
2
O
(l)
= -285.8
(a) Calculate H
rxn

(b) Calculate E at 25C

3. A styrofoam coffee cup serves as an inexpensive
calorimeter for measurements that do not require
high accuracy. To 25.0 mL of water in such a cup at
24.33C, a 1.00 g portion of KCl
(s)
was added. It
dissolved completely after a short period of gentle
stirring (using the thermometer). The minimum
temperature reached was 22.12C. Estimate H for
the heat of dissolution of KCl in kJ/mol. You may
assume that the solution has the same heat capacity
as the water (4.18 J/g K) and that the heat capacity of
the calorimeter itself is negligible.
[AW (g/mol): Cl 35.45, K 39.10]
Chemical Thermodynamics 2:
Spontaneity and Free Energy
The second law of thermodynamics states, In
spontaneous changes the universe tends towards a
state of greater disorder.


Spontaneous processes have two requirements:
1. The free energy change of the system must be negative.
2. The entropy of universe must increase.

2nd Law of Thermodynamics
Entropy, S
Entropy is a measure of the disorder or randomness
of a system.

As with AH, entropies have been measured and
tabulated in Appendix K as S
o
298
.

When:
AS > 0 disorder increases (which favors
spontaneity).
AS < 0 disorder decreases (does not favor
spontaneity).

Entropy, S
From the Second Law of Thermodynamics, for
a spontaneous process to occur:
0 S S S
gs surroundin system universe
> A + A = A
In general for a substance in its three states of matter:
S
gas
> S
liquid
> S
solid

Entropy, S
3rd Law of Thermodynamics
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.
To get the actual value of S, cool a substance to 0 K, or as
close as possible, then measure the entropy increase as
the substance heats from 0 to higher temperatures.
Notice that Appendix K has values of S not AS. THEY ARE
ABSOLUTE VALUES
Entropy Values
Standard states similar to enthalpy standard
states conditons

However, all substances at 25
o
C has NONZERO
ENTROPY values.

The reference state is the ABSOLUTE ZERO
temperature, 0 K.

Unit: J/K-mole
Entropy Values
Substance Entropy, S
o
, J/K-
mole
N
2(g)
191.61
Fe
(s)
27.28
Br
(l)
152.23
Cu
2+
(aq)
-99.6
Cs
1+
(aq)
133.05
CO
3
2-
(aq)
-56.9
H
+
(aq)
0
Entropy, S
Entropy changes for reactions can be determined
similarly to AH for reactions.
o
reactants
n
o
products
n
o
298
S n S n S

= A
Entropy, S
Example 1: Calculate the entropy change for
the following reaction at 25
o
C. Use values in
appendix K.

4(g) 2 2(g)
O N NO 2
K mol
kJ
K mol
J
K mol
J
K mol
J
o
NO
o
O N
o
reactants
n
o
products
n
o
rxn
0.1758 - or 8 . 175
) 0 . 240 ( 2 ) 2 . 304 (
S 2 S
S n S n S
2(g) 4(g) 2
=
=
=
= A

Entropy, S
Example 2: Calculate AS
o
298
for the reaction
below. Use values in appendix K.
( ) ( ) ( ) g 2 g 2 g
NO O N NO 3 +

( ) ( ) ( )
( ) | |
K mol
kJ
K mol
J
K mol
J
0
NO
0
NO
0
O N
0
298
0.1724 - or 4 . 172
210.4 3 - 240.0 7 . 219
S 3 S S S
g g 2 g 2
=
+ =
+ = A
What is Spontaneity?
Spontaneous changes happen without any
continuing outside influences.
A spontaneous change has a natural direction (you have to
consider the conditions of the system).
Gibbs Free Energy
The change in the Gibbs Free Energy, AG, is a reliable
indicator of spontaneity of a physical process or
chemical reaction.
AG does not tell us how quickly the process occurs. It will
only tell if a reaction is spontaneous or non spontaneous

AG is the Energy released to the surroundings (after
the spontaneous process of the system) to do useful
work!
Gibbs Free Energy: Sign
Convention
+

Free
Energy
0
G < 0, spontaneous
UNSTABLE
G = 0, system equilibrium, STABLE
SYSTEM
G > 0, nonspontaneous
Free energy
released to
the
surroundings
Energy must be
applied from the
surroundings
Gibbs Free Energy and
Reversibility
If a process is spontaneous i.e. one with highly
negative G, it will IRREVERSIBLY proceed to
give-off energy (thats why its called FREE
ENERGY)

Consider rusting of iron (Fe)
O
2
+ 4 e
-
+ 2 H
2
O 4 OH
-

Fe Fe
2+
+ 2 e


4 Fe
2+
+ O
2
4 Fe
3+
+ 2 O
2

2e
-
+ O
2-
+ 2H
2
O 4OH
-

Fe
3+
+ 3 H
2
O Fe(OH)
3
+ 3 H
+

Fe(OH)
3
FeO(OH) + H
2
O

2FeO(OH) Fe
2
O
3
+ H
2
O
Gibbs Free Energy and
Reversibility
Free
Energy
kJ/mole
Reaction pathway
Fe
(s)

, O
2(g)
, H
2
O
(l)


Fe
2
O
3(s)

G
Surroundings receives free
energy
RUST FORMATION wastes important materials and ENERGY!
Gibbs Free Energy and
Reversibility
Once an egg is broken, you need a lot of
external energy to put it together again!
Not Spontaneous!
WORK!
Free Energy Change, AG,
and Spontaneity
Changes in free energy obey the same type of
relationship we have described for enthalpy,
AH, and entropy, AS, changes.
Standard states also in 25
o
C and 1 atm
Elements in their standard forms also has ZERO
free energy change of formation (G
f
o
= 0, also
H
+
(aq)
)
All other properties is similar to Enthalpy and
Internal energy
0
reactants
n
0
products
n
0
298
G n G n G A A = A

Calculation of Free Energy Change
Example: Calculate AG
o
298
for the decomposition of
CaCO
3(s)
.
) ( 2(g) 3(s)
CaO CO CaCO
s
+
mol
kJ
mol
kJ
o
CaCO f
o
O Ca f
o
CO f
o
rxn
4 . 130
)} 8 . 1128 ( )] 0 . 604 ( ) 4 . 394 {[(
] G [ ] G G [ G
(s)
3 ) ( 2(g)
+ =
+ =
A A + A = A
s
Calculation of Free Energy Change
Example: Calculate AG
o
298
for the oxidation of glucose,
C
6
H
12
O
6(s).

) ( 2 2(g) 2(g) 6(s) 12 6
O 6H 6CO 6O O H C

+ +
mol
kJ
mol
kJ
o
O f
o
H H C f
o
O H f
o
CO f
o
rxn
2 . 2881
)]} 0 ( 6 ) 0 . 909 [( )] 3 . 237 ( 6 ) 4 . 394 ( 6 {[
] G 6 G [ ] G 6 G 6 [ G
2(g)
(s)
6 12 6 ) ( 2 2(g)
=
+ + =
A + A A + A = A

Very Spontaneous! But why are we still
alive? We should have been liquefied! :B
Activation energy prevents many spontaneous reactions from
happening immediately.
Calculation of Free Energy Change
Free Energy Calculations
Consider the formation of ice
- spontaneous only at low temp ( 0
o
C), but is
an ordered process (entropy decreases)


Free Energy, Disorder, and Enthalpy
A A A G = H - T S (at constant T & P)
G = H TS
Because 0 AH 0 and 0 AS 0, there are
four possibilities for AG.

AH AS AG Reaction spontaneity
+ Spontaneous at all Ts.
Temp dependent Spont at low
Temp.
+ Temp dependent Spont at high Temp.
+ + NON Spont at all Ts.
Calculations at Equilibrium
Example: Use thermodynamic data to estimate the
normal boiling point of water.

S
H
T and S T H Thus
0. G process m equilibriu an is this Because
O H O H
(g) 2 ) ( 2
A
A
= A = A
= A

Calculations at Equilibrium
Assumptions
Enthalpy of Vaporization at 25
o
C is the same as Enthalpy
of Vaporization at the boiling point
Entropy of Vaporization at 25
o
C is the same as Entropy
of Vaporization at the boiling point

| |
assume H@BP H
H H H
H
H kJ@25 C
298
o
o
H O
o
H O
o
o
J
K
o o
2 (g) 2 ( )
A A
A A A
A
A
~
=
=
= +
l
2418 2858
44 0
. ( . )
.
( ) ( )
| |
K
kJ
K
J
0
rxn
K
J
0
rxn
0
O H
0
O H
0
rxn
0
rxn
0.1188 or 8 . 118 S
91 . 69 7 . 188 S
S S S
S BP @ S assume
2 g 2
= A
= A
= A
A ~ A

Calculations at Equilibrium
Calculations at Equilibrium
T =
H
S
H
S
.0 kJ
0.1188
K
370 K-273 K=97 C
o
o
kJ
K
o
A
A
A
A
~ = =
44
370
( )
% error =
370- 373 K
K
error
% error of less than 1%!!
373
100% 080% = .
Coupled Reactions
First step in utilizing glucose (in all organisms)
Non spontaneous
Coupled
Reaction
Spontaneous, yeah!

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