Thermodynamics : Entropy

Entropy (S) - A measure of the disorder in a system. Entropy is a state function.

where k is a proportionality constant equal to the ideal gas constant (R) divided by Avogadro's number
(.!"" # $!
-"%
) and ln& is the natural log of &' the number of equivalent ways of describing the state of a
system.
(n this reaction' the number of ways of describing a system is directly proportional to the entropy of the
system.
Entropy of Reaction ( S)
)he difference between the sum of the entropies of the products and the sum of the entropies of
the reactants*
(n the above reaction' n and m are the coefficients of the products and the reactants in the balanced
equation.
Second Law of Thermodynamics
Natural processes that occur in an isolated system are spontaneous when they lead to an increase in
the disorder, or entropy, of the system.
Isolated system - +ystem in which neither heat nor wor, can be transferred between it and its
surroundings. )his ma,es it possible to ignore whether a reaction is e#othermic or endothermic.
(f Ssys > ' the system becomes more disordered through the course of the reaction
(f Ssys ! ' the system becomes less disordered (or more ordered) through the course of the reaction.
)here are a few basic principles that should be remembered to help determine whether a system is
increasing or decreasing in entropy.
-iquids are more disordered than solids.
o &./0 - +olids have a more regular structure than liquids.
1ases are more disordered than their respective liquids.
o &./0 - 1ases particles are in a state of constant random motion.
Any process in which the number of particles in the system increases consequently results in an
increase in disorder.
2oes the entropy increase or decrease for the following reactions0
$.
".
%.
3.
Answers*
$. IN"RE#SES - )he number of particles in the system increases' i.e. one particle decomposes into
two. (n addition' one of the products formed is a gas which is much more disordered than the
original solid.
". $E"RE#SES - )he number of particles in the system decreases' i.e. there are four moles of gas
reactants and only " moles of gas products.
%. IN"RE#SES - )he number of particles in the system increases' i.e. the single reactant dissociates
into two ion particles. (n addition' the ions in the ionic solid are organi4ed in a rigid lattice
structure whereas the ions in aqueous solution are free to move randomly through the solvent.
3. $E"RE#SES - )he reactant changes from a gas to a liquid' and gases are more disordered than
their respective liquids.
Third Law of Thermodynamics
The entropy of a perfect crystal is %ero when the temperature of a the crystal is e&ual to a'solute %ero
( ().
At ! 5' there is no thermal motion'
and if the crystal is perfect' there
will be no disorder
6nce the temperature begins to rise
above !' the particles begin to move
and entropy gradually increases as
the average ,inetic energy of the
particles increases.
&hen temperature reaches the
melting point of the substance ()m)'
there is an abrupt increase in
entropy as the substance changes
from a solid to a more disordered
liquid.
Again the entropy increases
gradually as the motion of the
particles increases until the
temperature reaches the boiling
point of the substance ()b). At this
point' there is another drastic
increase in entropy as the substance
changes from a confined liquid
particles to radom motion gas
particles.
Standard)State Entropy of Reaction ( S )
)he entropy of reaction at standard-state conditions.
Standard)state conditions
)he partial pressures of any gases involved in the reaction is !.$ 78a.
)he concentrations of all aqueous solutions are $ 7.
7easurements are also generally ta,en at a temperature of "9 : (";< 5)
Sample entropy of reaction calculations
*) "alculate the standard)state entropy for the followin+ reaction +i,en the followin+ information.
#lso, e-plain the si+n of S for the reaction.
"ompound S (./mol)()
=a:l(s) >".$%
=a
?
(aq) 9;.!
:l
-
(aq) 9.9
(n the balanced reaction above' one mole of =a:l yields one mole of =a
?
and one mole of :l
-
. &e find the
+ by subtracting the entropy of the reactant from the sum of the entropies of the products*
)he change in entropy for this reaction is positive. )he disorder of the system increases because the number
of particles increases as one solid reactant is converted into two aqueous particles. Also' the ions in the
ionic solid are positioned in a rigid lattice structure whereas the ions in solution are free to move around.
0) "alculate the standard)state entropy for the followin+ reaction +i,en the followin+ information.
#lso, e-plain the si+n of S for the reaction.
"ompound S (./mol)()
=6"(g) "3!.!
="63(g) %!3.";
(n the balanced reaction above' two moles of =6" combine to form one mole of ="63. &e find the +
by subtracting the entropy of the reactant from the entropy of the product*
)he change in entropy for this reaction is negative. )he disorder of the system decreases because the
number of particles decreases as two moles of gas reactant are converted to one mole of gas product.
Thermodynamics : Gibbs Free Energy
1i''s 2ree Ener+y (1) - )he energy associated with a chemical reaction that can be used to do wor,. )he
free energy of a system is the sum of its enthalpy (.) plus the product of the temperature (5elvin) and the
entropy (+) of the system*
2ree ener+y of reaction ( 1)
)he change in the enthalpy ( .) of the system minus the product of the temperature (5elvin)
and the change in the entropy ( +) of the system*
Standard)state free ener+y of reaction ( 1 )
)he free energy of reaction at standard state conditions*
Standard)state conditions
)he partial pressures of any gases involved in the reaction is !.$ 78a.
)he concentrations of all aqueous solutions are $ 7.
7easurements are also generally ta,en at a temperature of "9 : (";< 5)
Standard)State 2ree Ener+y of 2ormation ( 1f )
)he change in free energy that occurs when a compound is formed form its elements in their most
thermodynamically stable states at standard-state conditions. (n other words' it is the difference
between the free energy of a substance and the free energies of its elements in their most
thermodynamically stable states at standard-state conditions.
)he standard-state free energy of reaction can be calculated from the standard-state free energies
of formation as well. (t is the sum of the free energies of formation of the products minus the sum
of the free energies of formation of the reactants*
Recall from the enthalpy notes that reactions can be classified according to the change in enthalpy (heat)*
Endothermic - absorbs heat' . @ !
E-othermic - releases heat' . @ !
Reactions can also be classified according to the change in the free energy of the reaction*
Endothermic - =6=-+86=)A=E6A+' 1 @ !
E-othermic - +86=)A=E6A+' 1 B !
Summary
Cavorable
:onditions

Anfavorable
:onditions
. B ! . @ !
+ @ ! + @ !
DAne#pected End of Cormula(f a reaction is favorable for both enthalpy ( . B ! ) and entropy
( + @ !)' then the reaction will be +86=)A=E6A+ ( 1 B ! ) at any temperature.
(f a reaction is unfavorable for both enthalpy ( . @ ! ) and entropy ( + B ! )' then the
reaction will be =6=+86=)A=E6A+ ( 1 @ ! ) at any temperature.
(f a reaction is favorable for only one of either entropy or enthalpy' the standard-state free energy
equation must be used to determine whether the reaction is spontaneous or not.
Sample free ener+y calculation
"ompound
3f

S
=.3=6%(s) -%9.9 $9$.!<
=.3
?
(aq) -$%".9$ $$%.3
=6%
-
(aq) -"!9.! $3.3
"alculate 3 , S , and 1 for the a'o,e reaction to determine whether the reaction is
spontaneous or not.
Cirst let's calculate 3f . =ote that in the above reaction' one mole of =.3=6% dissociates in water to
give one mole each of =.3
?
and =6%
-
*
=e#t' let's calculate S *
=ow we can plug in these values we've calculated into the free energy equation.
N4TE5 )he units of 3f is 6. and the units of S is ./(. +ince 1 is generally reported
in 6.' we can divide S by $!!! to convert it to units of 6./(
N4TE5 )he temperature in the free energy equation must be in 5elvin' so we must convert the
given temperature in :elsius to 5elvin by adding ">%.$9.
Temperature and 2ree Ener+y
(f a reaction is favorable for enthalpy ( . B ! )' but unfavorable for entropy ( + B ! )' then
the reaction becomes -E++ +86=)A=E6A+ as temperature increases.
o &./0 - )he standard-state free energy equation states that*
(f entropy is unfavorable' the + is negative. +ubtracting a negative number is the
same as adding the respective positive number. As the temperature increases' the ) +
factor (which is A22E2 to the enthalpy if the entropy is unfavorable) increases as well.
Eventually' the ) + factor becomes larger than . and 1 becomes positive'
i.e. the reaction is no longer spontaneous.
Sample "alculations
"ompound
3f

S
="(g) ! $;$.$
."(g) ! $%!.<
=.%(g) -3.$$ $;".39
*) "alculate 3 and S for the a'o,e reaction. E-plain what each of the si+ns mean.
3 is negative which is favorable.
S is negative which is unfavorable.
0) 7redict whether the a'o,e reaction is spontaneous at 08 ".
1 is ne+ati,e, so the reaction is S74NT#NE49S.
:) 7redict whether the a'o,e reaction is spontaneous at 8 ".
1 is positi,e, so the reaction is N4T S74NT#NE49S.
2ree ener+y and E&uili'rium "onstants
)he following equation relates the standard-state free energy of reaction with the free energy of reaction at
any moment in time during a reaction (not necessarily at standard-state conditions)*
1 E free energy at any moment
1 E standard-state free energy
R E ideal gas constant E <.%$3 FGmol-5
) E temperature (5elvin)
lnH E natural log of the reaction &uotient
Reaction &uotient (;c or ;p) - )he mathematical product of the concentrations (or partial pressures) of the
products of a reaction divided by the mathematical product of the concentrations (or partial pressures)
reactants of a reaction #T #N< =4=ENT IN TI=E.
Note5 &hen Hc E 5c (or when Hp E 5p)' a reaction is at equilibrium.
(t was stated earlier that when 1 E !' a reaction is at equilibrium. -et's consider the above reaction at
equilibrium*
(f we move R)ln5 to the opposite side by subtracting it from both sides' we get the following reaction
which relates the free energy of a reaction to the equilibrium constant of a reaction*
Summary
S74NT#NE49S N4N)S74NT#NE49S
1 B !
5 @ $
1 @ !
5 B $
)he magnitude of 1 measures how far a reaction is from equilibrium. )he larger the value of 1 '
the further the reaction is from equilibrium and the further the reaction must shift to reach equilibrium. (n
reactions in which enthalpy is favorable and entropy is unfavorable' the reaction becomes less spontaneous
( 1 increases) until eventually the reaction is not spontaneous (when 1 @ !). As the magnitude of
1 changes' so does the equilibrium constant. 5.