Free Energy and Thermodynamics

Page 1 of 9

Natures Heat Tax

First Law of Thermodynamics
First Law of Thermodynamics: Energy cannot be created or destroyed
9 the total energy of the universe cannot change
9 though you can transfer it from one place to another
Euniv = 0 = Esys + Esurr

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

Spontaneous and Nonspontaneous Processes

Thermodynamics and Spontaneity
thermodynamics predicts whether a process will proceed under the given conditions
9 spontaneous process
nonspontaneous processes require energy input to go
spontaneity is determined by comparing the free energy of the system before the reaction with the
free energy of the system after reaction.
9 if the system after reaction has less free energy than before the reaction, the reaction is
thermodynamically favorable.
spontaneity fast or slow
The direction of spontaneity can be determined by comparing the potential energy of the system at
the start and the end.

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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

Thermodynamics vs. Kinetics

Practice 1 -. Which of the following processes are spontaneous?

a. The combustion of natural gas
b. The extraction of iron metal from iron ore
c.

A hot drink cooling to room temperature

d. Drawing heat energy from the oceans surface to power a ship

Entropy and the Second Law of Thermodynamics
Factors Affecting Whether a Reaction Is Spontaneous
The two factors that determine the thermodynamic favorability are the enthalpy and the entropy.
The enthalpy is a comparison of the bond energy of the reactants to the products.
9 bond energy = amount needed to break a bond. H
The entropy factors relates to the randomness/orderliness of a system. S
The enthalpy factor is generally more important than the entropy factor

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

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Changes in Entropy, S (S = Sfinal Sinitial.)

entropy change is favorable when the result is a more random system when S is positive.
Some changes that increase the entropy are:
9 reactions whose products are in a more disordered state. (solid < liquid < gas)
9 reactions which have larger numbers of product molecules than reactant molecules.
9 increase in temperature
9 solids dissociating into ions upon dissolving
The 2nd Law of Thermodynamics
the total entropy change of the universe must be positive for a process to be spontaneous
9 for reversible process Suniv = 0,
9 for irreversible (spontaneous) process Suniv > 0
Suniv = Ssys + Ssurr
if the entropy of the system decreases, then the entropy of the surroundings must increase by a
larger amount, i.e., when Ssys is negative, Ssurr becomes positive
the increase in Ssurr often comes from the heat released in an exothermic reaction
Entropy Change in State Change
when materials change state, the number of
macro-states it can have changes as well
9 for entropy: solid < liquid < gas
9 because the degrees of freedom of
motion increases
solid liquid gas

Heat Transfer and Changes in the Entropy of the Surroundings

Temperature Dependence of Ssurr
when a system/process is exothermic, it adds heat to the surroundings, increasing the entropy of the
surroundings
when a system process is endothermic, it takes heat from the surroundings, decreasing the entropy
of the surroundings
the amount the entropy change of the surroundings depends on the temperature it is at originally
9 the higher the original temperature, the less effect addition or removal of heat has

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.

Na(s) + C2(g) NaC(s)

d. N2(g) + 3 H2(g) 2 NH3(g)

Free Energy and Thermodynamics / Page 4 of 9

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

Gibbs Free Energy

maximum amount of energy from the system available to do work on the surroundings
G = H TS
G =
nG f (products )
mG f (reactants)
Gsys = Hsys TSsys

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

Free Energy Change and Spontaneity

Gibbs Free Energy, G
process will be spontaneous when G
is negative
G will be negative when
9 H is negative and S is positive:
exothermic and more random
9 H is negative and large and S is
negative but small
9 H is positive but small and S is
positive and large (or high
temperature)
G will be positive when H is + and
S is
9 never spontaneous at any
temperature
when G = 0 the reaction is at
equilibrium
G, H, and S

G = H TS

Free Energy Determines the Direction of Spontaneous Change

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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

The 3rd Law of Thermodynamics: Absolute Entropy

the absolute entropy of a substance is the amount of energy it has due to dispersion of energy
through its particles
the 3rd Law states that for a perfect crystal at absolute zero, the absolute entropy = 0 J/molK
9 every substance that is not a perfect crystal at absolute zero has some energy from entropy
9 the absolute entropy of substances is always +
So of a reaction

S =

nS (products) mS (reactants)

Example: Consider the reaction: N2(g) + 3 H2(g) 2 NH3(g)

So = {2So(NH3) [So(N2) + 3So(H2)]}

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)

Free Energy and Thermodynamics / Page 6 of 9

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.

Free Energy Changes in Chemical Reactions

Calculating G
at 25C:
Gorxn = nGof(products) mGof(reactants)
at temperatures other than 25C:
Grxn = Hrxn TSrxn
9 assuming the changes in Horxn and Sorxn are negligible
G Relationships
if a reaction can be expressed as a series of reactions, the sum of the G values of the individual
reaction is the G of the total reactionG is a state function
if a reaction is reversed, the sign of its G value reverses (similar to H)
if the amounts of materials is multiplied by a factor, the value of the G is multiplied by the same
factorthe value of G of a reaction is extensive (depends on amount)
note G is related to work energy while H is related to heat energy

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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)

Free Energy and Thermodynamics / Page 8 of 9

Practice 12 -. Consider the following reaction: 2 NO(g) + O2(g) 2 NO2(g)

Estimate G for this reaction at each of the following temperatures and predict whether or not the
reaction will be spontaneous a) at 298 K and b) at 855 K. (Assume that H and S do not change too
much within the given temperature range.)

Free Energy Changes for Nonstandard States G

under Nonstandard Conditions
G = G only when the reactants and products are in their standard states
o their normal state at that temperature (25 C)
o partial pressure of gas = 1 atm
o concentration = 1 M
under nonstandard conditions, G = G + RT lnQ, where Q is the reaction quotient
at equilibrium G = 0
o G = RT lnK; K = e(G/RT)
(Refer to Example 17.9 and Practice 17.9 for problem solving help and hint.)
Free Energy (Gorxn) and Equilibrium (K)
Temperature Dependence of K
for an exothermic reaction, increasing the temperature decreases the value of the equilibrium
constant
for an endothermic reaction, increasing the temperature increases the value of the equilibrium
constant
Vant Hoff Equation

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.)

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Practice 13 - Consider the sublimation of iodine at 25.0C: I2(s) I2(g)

a. Find Grxn at 25.0C.
b. Find Grxn at 25.0C under the following nonstandard conditions:
(i) PI2 = 1.00 mmHg
(ii) PI2 = 0.100 mmHg
c. Explain why iodine spontaneously sublimes in open air at 25.0C.