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Chemistry: The Central Science

Chapter 19: Chemical Thermodynamics

 Chemical thermodynamics – the area of chemistry that deals with energy

relationships

19.1: Spontaneous Processes

 First law of thermodynamics – energy is conserved

o Energy cannot be created or destroyed
o
 ΔE is the change in the internal energy
 q is the heat absorbed by the system from the surrounding
 w is the work done on the system by the surrounding
 Spontaneous process is one that proceeds on its own without any outside assistance
o Processes that are spontaneous in one direction are nonspontaneous in the
opposite direction
o A chemical reaction is spontaneous if it occurs on its own accord, regardless
of its speed
 Experimental conditions, such as temperature and pressure, are often important in
determining whether a process is spontaneous
o E.g. the melting of ice is spontaneous in room temperature and the freezing
of water is spontaneous below 0°C
 At the normal melting point of a substance, the solid and liquid phase
are in equilibrium
 Thermodynamics can tell us the direction and extent of a reaction but tells us nothing
about the speed of the reaction
 Seeking a Criterion for Spontaneity
o Spontaneous reactions are generally exothermic, with some spontaneous
endothermic reactions
o Temperature, internal energy, and enthalpy are state functions, properties
that define a state and do not depend on how we reach that state
 q and w are not state function
 One of the keys to understanding spontaneity is distinguishing
between reversible and irreversible paths between states
 Reversible and Irreversible Processes
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o Rudolph Clausis concluded that a special significance could be ascribed to the

ratio of the heat delivered to an ideal engine and the temperature at which it
is delivered, q/T
 He named this ratio entropy
o In a reversible process, a system is changed in such a way that the system and
surroundings can be restored to their original state by exactly reversing the
change
o An irreversible process is one that cannot simply be reversed to restore the
system and its surrounding to their original states
 A reversible change produces the maximum amount of work that can
be achieved by the system on the surroundings (wrev = wmax)
o Reversible processes are those that reverse direction whenever an
infinitesimal change is made in some property of the system
o A constant-temperature process is isothermal
o E.g. gas in the cylinder-and-piston arrangement below

 When the partition is removed, the gas expands spontaneously to fill

the evacuated space
 Because the gas is expanding into a vacuum with no external
pressure, it does no P-V work on the surrounding (w = 0)
 If the piston was used to compress the gas back to its original
state, it is required that the surrounding do work on the system
(w > 0)
 The fact that the system and the surrounding are not both returned to
their original conditions indicates that the process is irreverable
o The reverse of any spontaneous process is a nonspontaneous process
 Any spontaneous process is irreversible

19.2: Entropy and the Second Law of Thermodynamics

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 Entropy – the thermodynamic quantity associated with the extent of randomness in

a system or with the extent to which energy is distributed or dispersed among the
various motions of the moles of the system
 Entropy Change
o Entropy (S) of a system is a state function like the internal energy and
enthalpy

o For the special case of an isothermal process

 ΔS for Phase Changes
o Imagine that we melt one mole of ice at 0 °C, 1 atm to form one mole of liquid
water at 0 °C, 1 atm
 This change can be achieved by adding a certain amount of het to the
system from the surroundings: q = ΔHfusion
 Now imagine that we carry out the change by adding the heat infinitely
slowly, raising the temperature of the surroundings only infinitesimally
above 0 °C
 When we make the change in this fashion, the process is
reversible
 We can reverse the process simply by infinitely slowly removing
the same amount of heat, ΔHfusion, from the system
 The enthalpy of fusion of H2O us ΔHfusion = 6.01 kJ/mol

 The Second Law of Thermodynamics
o The entropy change of the system and the entropy change of the
surroundings when a mole of ice melts in the palm of your hand

 The surroundings immediately in contact with the ice are your hand,
which we will assume is at the body temperature 37 °C = 310 K
 The heat lost by your hand is gained by the ice

 The total entropy change is positive

 If it was an isothermal process, the entropy change of the surrounding
would equal -22.0 J/K and ΔStotal would be zero
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o Second law of thermodynamics – In general, any irreversible process results

in an overall increase in entropy, whereas a reversible process results in no
overall change in entropy
 The total entropy change is referred to as the entropy change of the
universe, ΔSuniv
 Reversible process:
Irreversible process:
 All spontaneous processes are irreversible
 Thus, the total entropy of the universe increases in any
spontaneous process

19.3: The Molecular Interpretation of Entropy

 Ludwig Boltzmann gave conceptual meaning to entropy

 Molecular Motions and Energy
o The higher the temperature, the faster the molecules are moving and the
more kinetic energy they possess
o Hotter systems have a broader distribution of molecular speeds
o Molecules can undergo three kinds of motion
 Translational motion – the entire molecule can move in one direction
 Vibrational motion – the atoms in the molecule move periodically
toward and away from one another, much as a tuning fork vibrates
about its equilibrium shape
 Rotational motion – the molecules spin like tops
 Below show some possible vibrational and rotational motion of water:

 Boltzmann’s Equation and Microstates

o Statistical thermodynamics – field of science that uses the tools of statistics
and probability to provide the link between the microscopic and macroscopic
worlds
o Positions of the gas molecules and their individual kinetic energies need to be
considered to understand how microscopic level processes relate to the
entropy of a sample
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o Imagine taking a snapshot of the positions and speeds of all the molecules a a
given instant
 That particular set of 6 × 1023 positions and energies of the individual
gas molecules is what we call a microstate of the thermodynamic
system
 Tools of statistics and probability can be used to determine the total
number of microstates for the thermodynamic state

 S is the entropy
 K is Boltzmann’s constant, 1.38 × 10-23 J/K
 W is the characteristic number of microstates associated with
each thermodynamic state
 Entropy is a measure of how many microstates are associated with a
particular macroscopic state
o The entropy change accompanying any process is

 Entropy increases with the number of microstates of the system
o In general, the number of microstates available to a system increases with an
increase in volume, an increase in temperature, or an increase in the number
of molecules
 Any of these changes increases the possible positions and energies of
the molecules of the system
o Chemists use several ways to describe an increase in the number of
microstates and therefore an increase in the entropy for a system
 Some say the increase in entropy represents an increase in the
randomness or disorder of the system
 Others liken an increase in entropy to an increased dispersion
(spreading out) of energy because there is an increase in the number
of ways the positions and energies of the molecules can be distributed
 Making Qualitative Predictions About ΔS
o In most instance, an increase in the number of microstates, and hence an
increase in entropy parallels an increase in: temperature, volume, number of
independently moving particles
o When an ionic solid, such as KCl, dissolves in water, a mixture of water an ions
replaces the pure solid and pure water
 The ions now move in a larger volume and possess more motional
energy than in the rigid solid
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 However, water molecules are held around the ions as water of

hydration
 The greater the charge of an ion, the greater are the ion-dipole
attractions that hold the ion and the water together
 Thus, although the solution process is normally accompanied by a net
increase in entropy, the dissolving of salts with highly charged ions can
result in a net decrease in entropy
o E.g.
 The formation of the new N—O bonds reduces the motions of the
atoms in the system
 The formation of the new bonds decreases the number of degrees of
freedom, or forms of motion, available to the atoms
 This reaction results in a decrease in entropy
o In summary, we generally expect the entropy of the system to increase for
processes in which
 Gases are formed from either solids or liquids
 Liquids or solutions are formed from solids
 The number of gas molecules increases during a chemical reaction
 The Third Law of Thermodynamics
o Third law of thermodynamics – the entropy of a pure crystalline substance at
absolute zero is zero
o As temperature increase from absolute zero, the entropy increases
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 There is a sharp increase at the melting point because the bonds

holding the atoms or molecule are broken
 There is another sharp increase in entropy at the boiling point as a
result of increased volume in which the molecules may be found
o Entropy generally increases with increasing temperature because the
increased motional energy can be dispersed in more ways
o The entropies of the phases of a given substance follow the order
 Ssolid < Sliquid < Sgas

19.4: Entropy Changes in Chemical Reactions

 Entropy are usually tabulated as molar quantities, in units of joules per mole-kelvin
(J/mol-K)
 The m0lar entropy values of substances in their standard states are known as
standard molar entropies (S°)
o Unlike enthalpies of formation, the standard molar entropies of elements at
the reference temperature of 298 K are not zero
o The standard molar entropies of gases are greater than those of liquids and
solids
o Standard molar entropies generally increase with increasing molar mass
o Standard molar entropies generally increase with an increasing number of
atoms in the formula of a substance

o The coefficients n and m are the coefficients in the chemical equation
 Entropy Changes in the Surroundings
o The surroundings serve essentially as a large, constant-temperature heat
source (or heat sink if the heat flows from system to surrounding)
 The change in entropy of the surroundings will depend on how much
heat is absorbed or given off by the system
o For an isothermal process, the entropy change of the surrounding is given by

 For a reaction occurring at constant pressure, qsys is simply the enthalpy
change for the reaction

 E.g. formation of ammonia from H2 (g) and N2 (g)

 At 298 K the formation of ammonia is exothermic

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o The magnitude of the entropy gained by the surrounding is greater than that
lost by the system
 ΔSouniv is positive for any spontaneous reaction
 When NH3, H2, and N2 are together at 298 K in their standard states,
the reaction system will move spontaneously toward formation of NH3

19.5: Gibbs Free Energy

 A spontaneous, endothermic process must be accompanied by an increase in the

entropy of the system
 Spontaneous processes that result in a decrease in the system’s entropy are always
exothermic
 J. Willard Gibbs proposed a new state function, now called the Gibbs free energy (or
just free energy)
o ΔG = ΔH – TΔS
 If ΔG is negative, the reaction is spontaneous in the forward direction
 If ΔG is zero, the reaction is at equilibrium
 If ΔG is positive, the reaction in the forward direction is
nonspontaneous; the reverse direction is spontaneous
o In any spontaneous process at constant temperature and pressure, the free
energy always decreases
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 Standard Free Energy of Formation

o We can tabulate standard free energies of formation for substances because
it is a state function
 Standard values for these function imply a particular set of conditions,
or standard states
 Standard state for gaseous substance is 1 atm pressure
 Standard state for solid is pure solid
 Standard state for liquid is pure liquid
 For substance in solution, the standard state is normally a
concentration of 1 M
o The standard free energies of formation are useful in calculating the standard
free-energy change for chemical processes


19.6: Free Energy and Temperature

 When the sign of ΔH < 0 and sign of ΔS > 0, ΔG is negative and the reaction is
spontaneous at all temperature
 When the sign of ΔH > 0 and sign of ΔS < 0, ΔG is positive and the reaction is
nonspontaneous at all temperature
 When the sign of ΔH and ΔS is the same, the reaction’s spontaneity depends on
temperature

19.7: Free Energy and the Equilibrium Constant

 At equilibrium ΔG = 0
 Value of ΔG cab be calculated from ΔG°
o
 R is the ideal gas constant, 8.314 J/mol-K
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 T is the absolute temperature

 Q is the reaction quotient that corresponds to the particular reaction
mixture of interest
 The concentrations of gases are always expressed by their
partial pressure in atmospheres
 Solutes are expressed by their concentration in molarity
 Relationship between ΔG° and K
o

 ΔG° is expressed in kJ/mol
 If ΔG° is positive, K is negative
 If ΔG° is negative, K is positive