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Conservation of Energy
For an exothermic reaction, lost heat from the system goes into the surroundings
two ways energy lost from a system,
9 converted to heat, q
9 used to do work, w
Energy conservation requires that the energy change in the system equal the heat released + work
done
9 E = q + w
9 E = H + PV
E is a state function
9 internal energy change independent of how done
Energy Tax
to recharge a battery with 100 kJ of useful energy will require more than 100 kJ
every energy transition results in a loss of energy
9 conversion of energy to heat which is lost by heating up the surroundings
Reversibility of Process
any spontaneous process is irreversible
9 it will proceed in only one direction
a reversible process will proceed back and
forth between the two end conditions
9 equilibrium
9 results in no change in free energy
if a process is spontaneous in one direction,
it must be nonspontaneous in the opposite
direction
Enthalpy
related to the internal energy
H generally kJ/mol
stronger bonds = more stable molecules
if products more stable than reactants, energy released
9 exothermic
9 H = negative
if reactants more stable than products, energy absorbed
9 endothermic
9 H = positive
The enthalpy is favorable for exothermic reactions and unfavorable for endothermic reactions.
Hess Law Hrxn = (Hprod) (Hreact)
Entropy
entropy is a thermodynamic function that increases as the number of energetically equivalent ways
of arranging the components increases, S, generally J/mol
S = k ln W
k = Boltzmann Constant = 1.38 x 1023 J/K
W is the number of energetically equivalent ways, unit-less
Random systems require less energy than ordered systems
Ssurroundings =
H system
T
Practice 2 - Without doing any calculations, determine the sign ofSsys for each of the following chemical
reactions:
a. 2 KCO3(s) 2 KC(s) + 3 O2(g)
b. CH2=CH2(g) + H2(g) CH3CH3(g)
c.
Practice 3 -. Without doing any calculations determine the sign of Ssys and Ssurr for each of the chemical
reactions below. In addition, predict under what temperatures (all temperatures, low temperatures, or
high temperatures), if any, the reaction will be spontaneous.
a. C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g) Hrxn = 2044 kJ
b. 2 N2(g) + O2(g) 2 N2O (g)
Hrxn = +163.2 kJ
when G < 0, there is a decrease in free energy of the system that is released into the surroundings;
therefore a process will be spontaneous when G is negative
G = H TS
Practice 4 - Calculate the free energy change for the following reaction at 25C. Is the reaction spontaneous?
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)
Hrxn = 2217 kJ; Srxn = 101.1 J/K
Practice 5 - Fill in the banks in the table below where both H and S refer to the system.
H S
G
Low Temperature High Temperature
a)
spontaneous
b)
Temp. dependent
c)
+
+
spontaneous
d)
nonspontaneous
nonspontaneous
Entropy Changes in Chemical Reactions, Sorxn
Standard Entropies, S (extensive property)
entropies for 1 mole at 298 K for a particular state, a particular allotrope, particular molecular
complexity, a particular molar mass, and a particular degree of dissolution
the gas state has a larger entropy than the liquid state at a particular temperature
the liquid state has a larger entropy than the solid state at a particular temperature
the larger the molar mass, the larger the entropy
larger, more complex molecules generally have larger entropy
dissolved solids generally have larger entropy
distributing particles throughout the mixture
S =
nS (products) mS (reactants)
Practice 6 -. For each pair of substances, choose the one that you expect to have the higher standard
molar entropy (S) at 25C. Explain the reasons for your choice.
b. CH3OH(l);
a. CO(g);
CH3OH(g)
CO2(g)
d. CH4(g);
c. Ar(g);
CO2(g)
SiH4(g)
f. NaBr(s);
e. NO2(g);
NaBr(aq)
CH3CH2CH3(g)
Practice 7 -. Rank each of the following in order of increasing standard molar entropy (S). Explain your
reasoning.
a. NH3(g); Ne(g); SO2(g); CH3CH2OH(g); He(g)
b. H2O(s); H2O(l); H2O(g)
c. CH4(g); CF4(g); CC4(g)
Practice 8 -. Use data from Appendix IIB to calculate Srxn for each of the reactions given below. In each
case, try to rationalize the sign of Srxn.
b. C(s) + H2O(g) CO(g) + H2(g)
a. C2H4(g) + H2(g) C2H6(g)
d. 2 H2S(g) + 3 O2(g) 2 H2O(l) + 2 SO2(g)
c. CO(g) + H2O(g) H2(g) + CO2(g)
Practice 9 -. Find S for the formation of CH2C2 from its elements in their standard states.
Rationalize the sign of S.
the change in free energy is a theoretical limit as to the amount of work that can be done
if the reaction achieves its theoretical limit, it is a reversible reaction
(Refer to Example 17.5-8 and Practice 17.5-8 for problem solving help and hint.)
Practice 10 -. Methanol burns in oxygen to form carbon dioxide and steam. Write a balanced equation
for the combustion of methanol and calculate Hrxn, Srxn, and Grxn at 25C. Is the combustion of
methanol spontaneous?
Practice 11 -. For each of the following reactions, calculate Hrxn, Srxn, and Grxn at 25C and state
whether or not the reaction is spontaneous. If the reaction is not spontaneous, would a change in
temperature make it spontaneous? If so, what is the temperature and will it need to be increased or
decreased to achieve spontaneity?
a. N2O4(g) 2 NO2(g)
b. NH4C(s) HC(g) + NH3(g)
c. 3 H2(g) + Fe2O3(s) 2 Fe(s) + 3 H2O(g)
d. N2(g) + 3 H2(g) 2 NH3(g)
ln K =
H orxn
R
1 Srxn
+
R
T
o
(Refer to Example 17.10 and Practice 17.10 for problem solving help and hint.)