Академический Документы
Профессиональный Документы
Культура Документы
Enthalpy, Entropy
& Gibbs Free
Energy
Thermo 2
×Ø
WORK
Thermo 6
EXAMPLES:
C(graphite, s) + O2 (g) CO2 (g)
ΔH°rxn = 0 kJ/mol 0 kJ/mol 393.5 kJ/mol
product
elements in their (one mole)
standard states
negative sign
heat released -- exothermic rxn ΔH°f (CO2 ) = 393.5 kJ/mol
Thermo 9
Note that we usually will not have you calculate ΔHfº on homeworks or
tests – so you generally don’t have to worry about normalizing your
answer to a per mole basis.
REACTANTS PRODUCTS
You can also add two reactions together to get the ΔHrxn for
another new reaction:
Calculate ΔH°rxn for the following reaction:
How to solve:
1) C 2 H 5 OH is on the product side of the first reaction -- so we want to
switch equation a) around to get C 2 H 5 OH also on the product side:
2) Now we can add the two reactions together to give us the desired
net reaction:
1
2CO2 (g) + 3H 2 O(l) C 2 H 5 OH(l) + 3O 2(g) ΔH°rxn = +1367 kJ/mol
Bomb Calorimeter
Electrical
contacts
to initate Thermocouple
Stirrer sample to measure
combustion temperature
Sample
placed
inside
inner
container
Water
Entropy
The final state of a system is more energetically
favorable if:
1. Energy can be dispersed over a greater number
and variety of molecules.
2. The particles of the system can be more
dispersed (more disordered).
The dispersal of energy and matter is described by
the thermodynamic state function entropy, S.
The greater the dispersal of energy or matter in a
system, the higher is its entropy. The greater the
disorder (dispersal of energy and matter, both in
space and in variety) the higher the entropy.
Adding heat to a material increases the disorder.
Ice - well ordered structure
150
phase transitions
100
50
0
Temperature (K)
H C H S° = 186 J/K•mol
H Methane
H C C H
Acetylene
S° = 201 J/K•mol
H H
C C Ethylene S° = 220 J/K•mol
H H
H H
H C C H S° = 230 J/K•mol
H H Ethane
H H H
H C C C H S° = 270 J/K•mol
H H H Propane
d) H2O(s) H2O(l)
e) graphite diamond
k) 2NO2(g) N2O4(g)
Thermo 20
REACTANTS PRODUCTS
Spontaneous Processes
A process that takes place without the net input of
energy from an external source is said to be
spontaneous (not instantaneous).
1) Rxn of sodium metal with water:
2Na(s) + 2H2O 2Na+(aq) + 2OH-(aq) + H2(g)
2) Combustion rxns:
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(g)
2H2(g) + O2(g) 2H2O(l)
ΔG = ΔH − TΔS
ΔS
+
Δ G = negative Δ G = ??
spontaneous spontaneous
at all temperatures at high temperatures
- 0 + ΔH
Δ G = ?? Δ G = positive
spontaneous non-spontaneous
at low temperatures at all temperatures
-
Spontaneous = exoergic (energy releasing)
Non-spontaneous = endoergic (energy releasing)
Thermo 25
DANGER!!
Common
mistake!!
Thermo 26
EXAMPLE:
2Mg(s) + CO 2 (g) 2MgO(s) + C(s)
ΔG°f = 0 kJ/mol - 394 kJ/mol - 570 kJ/mol 0 kJ/mol
REACTANTS PRODUCTS
SPONTANEOUS rxn!
ΔG°rxn = 746 kJ } highly exothermic rxn !!
Compare to Δ H °rxn which was -811 kJ for the same rxn.
T = (ΔH°rxn) / (ΔS°rxn)
T = (465 kJ/mol) / (0.552 kJ/molK)
T = 842 K
(above this temperature ΔG°rxn will be negative – we will have
a spontaneous reaction)
Thermo 30
From “General Chemistry”, 7th Ed, by Whitten, Davis, Peck & Stanley. Thomson Brooks/Cole Publisher.