Lecture PowerPoint Slides

to accompany

CHEMISTRY
Human Activity,
Chemical Reactivity

Prepared by
Philip Elder, Ph.D.

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 Chapter 17

Spontaneous Change:
How Far?

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Spontaneous Change: How Far?

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 Photochemical Smog and Chemical
Equilibrium
For many decades, London, England, was famous for its
pea-soupersa haze due to foggy atmospheric
conditions and smoke from industry and homes
(Smog = smoke + fog).
The deaths of 4000 Londoners were attributed to a
four-day smog in 1952.
Around the world, many cities have photochemical
smog problems, which result from dramatically
increasing populations, demands for industrial
products, and dependence on motor vehicles.

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 Photochemical Smog and Chemical
Equilibrium
Photochemical smogs are the result of a complicated
series of chemical reactions among substances
including mainly NO2(g), formed from NO(g), and VOCs
(volatile organic compounds) in an atmospheric soup.
uv light
NO + O2 + VOCs HNO3 + O3 + organic peroxides

To minimize smog formation, we need to understand

the distinction between thermodynamics and kinetics,
which are independent factors affecting a chemical
reaction.
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 Spontaneous Direction of Change
and Equilibrium
Spontaneous refers to the direction of reaction
that would take a reaction mixture closer to a
state of chemical equilibrium.
Spontaneous reactions may be extremely fast or
so slow that change is undetectable.
A decrease of enthalpy of the reaction mixture is
not a sufficient criterion to determine whether a
process is spontaneous.

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 Enthalpy Change of Reaction vs.
Spontaneity
EXAMPLES:
Dissolving NH4NO3(s) in water
is spontaneous and
endothermic.
The melting of ice above 0C is
endothermic.
Gas expanding into a vacuum
is endothermic and is the basis
of refrigeration.

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 Entropy: Dispersal of Energy and
Matter
To predict whether a process is spontaneous, we
can use a thermodynamic property called
entropy (S).
The concept of entropy is built on the idea that
spontaneous change results in dispersal of
energy.
The Second Law of Thermodynamics: Any
spontaneous process is accompanied by an
increase in the entropy of the universe.
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 Entropy: Dispersal of Energy and
Matter
Maximization of Entropy as Most Probable
Dispersal of Matter
The expansion of neon
gas over two flasks.
There are four possible
arrangements for two
atoms in this apparatus.
There is a 50% probability
that there will be one
atom in each flask at any
instant of time.
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 Entropy: Dispersal of Energy and
Matter
For gases at room temperature, the entropy-
driven dispersal of matter is equivalent to an
increase in disorder of the system.
EXAMPLE: Dissolution of KMnO4(s) in water

time

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 Entropy: Dispersal of Energy and
Matter
The formation of a mixture does not always lead
to greater disorder.
EXAMPLE: Aquation of lithium hydroxide

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 Entropy: Dispersal of Energy and
Matter
Maximization of Entropy as Most Probable
Dispersal of Matter
Maximization of entropy of a system
corresponds with the maximum probability of
distribution of matterthe system of least order.
Achieving maximum entropy is hindered by
energy constraints, such as bonds or
intermolecular forces.

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 Entropy: Dispersal of Energy and
Matter
The Boltzmann Equation for Entropy

The Boltzmann Equation for

entropy states:
S = k log W
where k is the Boltzmann
constant, and W represents the
number of different ways that
the energy can be distributed
over the available energy levels.
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 Entropy and the Second Law of
Thermodynamics
Entropy (S) is a measure of the lack of order
resulting from dispersal of energy and matter.
qrev
S
T
The reference point for entropy is provided by
The Third Law of Thermodynamics: There is no
disorder in a perfect crystal at 0 K, or S = 0.
All substances have positive entropy values at
temperatures above 0 K.
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 Entropy and the Second Law of
Thermodynamics
The standard molar entropy (S) of a substance
is the entropy of 1 mol of a substance in its
standard state at a specific temperature.
When comparing the same or similar substances,
the molar entropies of gases are much larger
than those for liquids, and the molar entropies
of liquids are larger than those for solids.

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Standard Molar Entropies of Some
Substances at 298 K

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 Entropy and the Second Law of
Thermodynamics

The entropy of liquid The entropy of ice, which has a

bromine is 152.2 J K1 mol1, highly ordered molecular
and bromine vapour is arrangement, is smaller than
245.47 J K1 mol1. that for liquid water.
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 Entropy and the Second Law of
Thermodynamics
Standard Molar Entropy of Substances, S
Substances composed of large molecules have higher
molar entropy than substances with smaller molecules.
Substances whose molecules have complex structures
have more entropy than those with simpler molecules.

EXAMPLES: Standard entropies (J K1 mol1)

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 Entropy and the Second Law of
Thermodynamics
Comparing two systems with the same number of
atoms of each element, and in the same phase, the one
with more, smaller molecules has more entropy.
EXAMPLE: at 25C and 1 bar,
The entropy of 1 mol of N2O4(g) is 304.38 J K1
The entropy of 2 mol of NO2(g) is 480.08 J K1

The entropy of any substance increases as the

temperature is raised. Large increases in entropy
accompany changes of state.

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 Entropy and the Second Law of
Thermodynamics
EXAMPLE: Entropy changes with increasing temperature

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 Entropy and the Second Law of
Thermodynamics
Standard Entropy Change of Reaction (rS)
The standard entropy change of a reaction (rS) at
a specified temperature at a specified temperature is
the difference between the sum of the standard
molar entropies of products and the standard molar
entropies of reactants (at that temperature) taking
into account the amounts of the products and
reactants shown in the balanced chemical equation:

rS = ni S(products) ni S(reactants)

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 Entropy and the Second Law of
Thermodynamics
EXAMPLE: Calculate the rS at 25C for the
oxidation of NO(g) by O2(g).
2 NO(g) + O2(g) 2 NO2(g)

rS = [2 S(NO2, g)] [2 S(NO, g) + S(O2, g)]

= [2 240.0 J K1 mol1] [(2 210.8 K1 mol1)
+ 205.1 K1 mol1)]
= 480.0 J K1 mol1 626.7 J K1 mol1
= 146.7 J K1 mol1
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Entropy Changes and Spontaneity
The criterion of spontaneity of a defined direction of
reaction is given by the second law of
thermodynamics: A spontaneous process is one that
results in an increase of entropy in the universe.
Suniv = Ssys + Ssurr

The standard entropy change at any specified

temperature can be expressed as:

Suniv = Ssys + Ssurr

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 Entropy Changes and Spontaneity
Contributions of rS and rH to Spontaneity of
Reaction
There are four different categories of reaction,
depending on the signs of Ssys and Ssurr , that govern
what we can say about the spontaneity of a reaction.

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 Entropy Changes and Spontaneity
Thermodynamics, Time, and Life
Because the entropy of the universe is always increasing,
it has been called times arrow.
Although neither the first or second law has been
proven experimentally, there has never been an example
demonstrating that either is false.
Living systems include many examples of localized
decreases of entropy, but these are offset by larger
increases of entropy in the rest of the universe.

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 Gibbs Free Energy
J. Willard Gibbs (18391903) made profound
contributions to thermodynamics and received the first
PhD in science awarded by an American university.
Gibbs was highly esteemed by his
friends, but American science was too
preoccupied with practical questions to
make much use of his profound
theoretical work during his lifetime. He
lived out his quiet life at Yale, deeply
admired by a few able students but
making no immediate impression on
American science commensurate with
his genius.J.G. Crowther (1969)
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 Gibbs Free Energy
The Gibbs free energy (G) can be used to identify
a spontaneous reaction as a single quantity. At a
specified temperature T, the free energy is
defined mathematically as:
G = H TS
The Free Energy Change of Reaction (rG) at any
stage in the reaction can be defined as the
following:
rG = ni G (products) ni G (reactants)
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 Gibbs Free Energy
rG = ni G (products) ni G (reactants)
However, this equation cannot be used to calculate rG
since the molar free energies of substances are not
known.
rG changes as the amounts of reactants and products
change during chemical reaction.
This equation for rG is an approximation because,
the free energy of 1 mol of a substance depends on its
pressure (if it is a gas) or concentration (if it is in solution), and
there is another contribution to rG due to mixing of the
reactants and products.
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 Gibbs Free Energy
rG and Spontaneity of Reaction
The second law states that a reaction is spontaneous if
Suniv > 0. A more convenient definition of reaction
spontaneity is as follows:
rG
Suniv
T
If rG < 0, the reaction is spontaneous as written.
If rG = 0, the reaction is at equilibrium.
If rG > 0, the reaction is not spontaneous (but
reaction in the opposite direction is).
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 Gibbs Free Energy
Change of free energy of a reaction mixture during
reaction.

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 Gibbs Free Energy
At any instant during a chemical reaction held at
constant temperature and pressure,
rG = rH TrS
In the particular case of a reaxtino mixture, in
which all reactants and products are in their
standard states, the free energy change of
reaction is the Standard Free Energy Change of
Reaction (rG)
rG = rH TrS
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 Gibbs Free Energy
For any reaction, rG can be calculated from the
values of rH and TrS

e17.11e17.12 Explore the relationships among rH, rS, and

rG.

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 Gibbs Free Energy
The Standard Molar Free Energy Change of
Formation (fG) of a compound is the standard
free energy change when 1 mol of the
compound is formed from its component
elements in their standard states.
By definition, the standard molar free energy
change of formation of an element in its
standard state is zero.
See Appendix D for a list of fG values.
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 Gibbs Free Energy
The standard free energy change of a reaction
can be calculated from fG of reactants and
products using the following equation:
rG = ni fG (products) ni fG (reactants)

In any process, the free energy change is the

maximum energy that becomes available to do
useful work. Mathematically,
rG = wmax

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 Gibbs Free Energy
Direction of spontaneous reaction in a standard-
state reaction mixture where rG < 0.
K > 1, the reaction is product-favoured

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 Gibbs Free Energy
Direction of spontaneous reaction in a standard-
state reaction mixture where rG > 0.
K < 1, the reaction is reactant-favoured

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 Gibbs Free Energy
Dependence of rG and Spontaneity of Reaction
on Temperature
rH and rS can be assumed temperature
independent over moderate changes of temperature.
For a reaction in which either
(a) rH < 0 and rS < 0, or
(b) rH > 0 and rS > 0,
a temperature can be calculated based on rG = rH
T rS, at which rG = 0. At this temperature, the
mixture is at equilibrium, and the direction of
spontaneous reaction differs on either side.
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 Gibbs Free Energy
Free Energy Change of Reaction in Non-standard
Reaction Mixtures
In practice, very seldom do reaction mixtures have all
species in their standard states. The magnitude of the
difference between the free energies of reaction is as
follows:
rG = rG + RT ln Q
Where R is the universal gas constant, and T is the
temperature in K.
If Q = 1, rG = rG
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The Relationship Between rG and K
For a specified reaction, rG and K at the same
temperature are mathematically,
0 = rG + RT ln K
rG = RT ln K
This equation allows calculation of an equilibrium
constant at the same temperature as thermochemical
data in tables or obtained from an experiment.
It provides a direct route to determine rG from
experimentally determined equilibrium constants.

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 rG and Ecell for Voltaic Cell
Reactions
We have seen that the standard cell emf (Ecell) is
a measure of the driving force of an overall
reaction taking place inside a voltaic cell.
For reactions that take place in a voltaic cell, the
standard free energy of reaction can also be
related to the cell emf as follows:
rG = nFEcell

e17.18 Calculate rG from Ecell

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 rG and Ecell for Voltaic Cell
Reactions
Related Driving Forces of Reaction: rG, K and
Ecell

For a spontaneous
reaction in a standard-
state mixture (Q = 1),
K > 1, Ecell > 0, and
rG < 0.

e17.19 Calculate rG and the equilibrium constant K from Ecell.

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 Dependence of Equilibrium
Constants on Temperature
Although each of the relationships in this chapter
apply at any temperature, all of the examples
occurred at 25C.
For any reaction, rG and K vary as temperature
changes, so we need to relate these values.
The dependence of the equilibrium constant on
temperature is given by the following
relationship o o
rH r S
lnK
RT R
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 Dependence of Equilibrium
Constants on Temperature
Dependence of K of a Reaction on Temperature.

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

Experimental data fit
closely to a straight line
relationship between ln K
and 1/T.

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 Dependence of K on Change of
Temperature
For an exothermic reaction (rHo negative), an increase of
T brings about a smaller value of ln K, and of K.
For an endothermic reaction, increase of T increases K.

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 Dependence of Equilibrium
Constants on Temperature
The vant Hoff equation can be used to estimate
K at one temperature from an experimentally
measured value at another temperature
rHo 1 1
lnK1 lnK2
R T1 T2

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 Dependence of Equilibrium Vapour
Pressures on Temperature
The dependence of equilibrium vapour pressures
of liquids and solids on temperature is a particular
case of dependence of equilibrium constants on
temperature and corresponding mathematical
relationships apply.
EXAMPLE: vap Go RTl np
Consider the equilibrium vap H o vap S o
between a liquid and its l np
RT
R
vapour at a defined vap H o 1 1
temperature l np1 l np2
R T1 T2
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 Photochemical Smog and the
Dependence of K on T
Primary pollutants are substances that have
been directly admitted to the atmosphere.
Secondary pollutants are substances formed by
the chemical reactions of primary pollutants.
The reactions that convert primary pollutants
into secondary pollutants are initiated by
absorption of radiant energy from the sun
hence, the label photochemical.

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 Photochemical Smog and the
Dependence of K on T
If a layer of cold air, perhaps polluted, is more dense
than the air above it, it remains trapped near ground
level. This cold layer acts as a reaction vessel, and after
absorbing energy from the sun, pollutants react with
each other.

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 Photochemical Smog and the
Dependence of K on T
Conditions that are most suited to formation of
photochemical smog:
High concentrations of nitrogen oxides and VOCs.
Thermal inversion.
Relatively still conditions so that the pollutants are
not swept away and diluted by winds.
Long periods of relatively intense sunlight.

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 Photochemical Smog and the
Dependence of K on T

The photochemical cycle

in the absence of VOCs,
initiated by photo-
decomposition of NO2,
maintaining low levels of
the reactive species O,
O3, NO, and NO2.

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 Photochemical Smog and the
Dependence of K on T
Typical diurnal (time-of-day) sequential build-up and decay
of important species in a photochemical smog.

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 Photochemical Smog and the
Dependence of K on T
OH radicals are formed
in the atmosphere by
reaction between O
atoms in an excited
state with H2O
molecules.
They are very reactive
as oxidizing agents.

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 Photochemical Smog and the
Dependence of K on T
The overall result of the multitude of reactions
leading to photochemical smogs is the
synergistic oxidation of NO and VOCs.
Oxidation of neither NO nor VOCs would occur
without the presence of the other.
NO(g) is formed in combustion chambers where the
temperature is high enough that the equilibrium
constant for its formation from N2(g) and O2(g) is
significant!

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