First Law of Thermodynamics

• You will recall that energy cannot be

created nor destroyed.
• Therefore, the total energy of the
universe is a constant.
• Energy can, however, be converted
from one form to another or transferred
from a system to the surroundings or
vice versa.
Chemical
Thermodynamics
 Spontaneous Processes
• Spontaneous processes
are those that can
proceed without any
outside intervention.
• The gas in vessel B will
spontaneously effuse into
vessel A, but once the
gas is in both vessels, it
will not spontaneously
Chemical
Thermodynamics
Spontaneous Processes

Processes that are

spontaneous in one
direction are
nonspontaneous in
the reverse
direction.

Chemical
Thermodynamics
 Spontaneous Processes
• Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
• Above 0C it is spontaneous for ice to melt.
• Below 0C the reverse process is spontaneous.

Chemical
Thermodynamics
Reversible Processes
In a reversible process
the system changes in
such a way that the
system and
surroundings can be
put back in their original
states by exactly
reversing the process.

Changes are
infinitesimally small in
a reversible process.

Chemical
Thermodynamics
 Irreversible Processes

• Irreversible processes cannot be undone by

exactly reversing the change to the system.
• All Spontaneous processes are irreversible.
• All Real processes are irreversible.
Chemical
Thermodynamics
 Entropy

• Entropy (S) is a term coined by Rudolph

Clausius in the 19th century.
• Clausius was convinced of the
significance of the ratio of heat
delivered and the temperature at which
it is delivered, q
T

Chemical
Thermodynamics
 Entropy

• Entropy can be thought of as a measure

of the randomness of a system.
• It is related to the various modes of
motion in molecules.

Chemical
Thermodynamics
 Entropy

• Like total energy, E, and enthalpy, H,

entropy is a state function.
• Therefore,
S = Sfinal  Sinitial

Chemical
Thermodynamics
 Entropy
• For a process occurring at constant
temperature (an isothermal process):

qrev = the heat that is transferred when the

process is carried out reversibly at a constant
temperature.
T = temperature in Kelvin.
Chemical
Thermodynamics
Second Law of Thermodynamics
The second law of thermodynamics:
The entropy of the universe does not
change for reversible processes
and
increases for spontaneous processes.
Reversible (ideal):

Irreversible (real, spontaneous):

Chemical
Thermodynamics
Second Law of Thermodynamics
“You can’t break even”

Reversible (ideal):

Irreversible (real, spontaneous):

Chemical
Thermodynamics
Second Law of Thermodynamics
The entropy of the universe increases (real,
spontaneous processes).
But, entropy can decrease for individual systems.
Reversible (ideal):

Irreversible (real, spontaneous):

Chemical
Thermodynamics
Entropy on the Molecular Scale
• Ludwig Boltzmann described the concept of
entropy on the molecular level.
• Temperature is a measure of the average
kinetic energy of the molecules in a sample.

Chemical
Thermodynamics
 Entropy on the Molecular Scale
• Molecules exhibit several types of motion:
 Translational: Movement of the entire molecule from
one place to another.
 Vibrational: Periodic motion of atoms within a molecule.
 Rotational: Rotation of the molecule on about an axis or
rotation about  bonds.

Chemical
Thermodynamics
 Entropy on the Molecular Scale
• Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.
 This would be akin to taking a snapshot of all the
molecules.
• He referred to this sampling as a microstate of the
thermodynamic system.

Chemical
Thermodynamics
 Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
microstates, W, associated with it.
• Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38  1023 J/K.

Chemical
Thermodynamics
 Entropy on the Molecular Scale
Implications:

• more particles
-> more states -> more entropy
• higher T
-> more energy states -> more entropy
• less structure (gas vs solid)
-> more states -> more entropy

Chemical
Thermodynamics
Entropy on the Molecular Scale
• The number of microstates and,
therefore, the entropy tends to increase
with increases in
Temperature.
Volume (gases).
The number of independently moving
molecules.

Chemical
Thermodynamics
 Entropy and Physical States

• Entropy increases with

the freedom of motion
of molecules.
• Therefore,
S(g) > S(l) > S(s)

Chemical
Thermodynamics
 Solutions
Dissolution of a solid:
Ions have more entropy
(more states)
But,
Some water molecules
have less entropy
(they are grouped
around ions).

Usually, there is an overall increase in S.

(The exception is very highly charged ions that Chemical
Thermodynamics
make a lot of water molecules align around them.)
 Entropy Changes

• In general, entropy
increases when
 Gases are formed from
liquids and solids.
 Liquids or solutions are
formed from solids.
 The number of gas
molecules increases.
 The number of moles
increases. Chemical
Thermodynamics
Third Law of Thermodynamics
The entropy of a pure crystalline
substance at absolute zero is 0.

Chemical
Thermodynamics
 Third Law of Thermodynamics
The entropy of a pure crystalline
substance at absolute zero is 0.

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Chemical
Thermodynamics
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 Standard Entropies

• These are molar entropy

values of substances in
their standard states.
• Standard entropies tend
to increase with
increasing molar mass.

Chemical
Thermodynamics
 Standard Entropies

Larger and more complex molecules have

greater entropies.

Chemical
Thermodynamics
 Entropy Changes

Entropy changes for a reaction can be

calculated the same way we used for H:

S° for each component is found in a table.

Note for pure elements:

Chemical
Thermodynamics
Practical uses: surroundings & system
Entropy Changes in Surroundings
• Heat that flows into or out of the system
also changes the entropy of the
surroundings.
• For an isothermal process:

Chemical
Thermodynamics
Practical uses: surroundings & system
Entropy Changes in Surroundings
• Heat that flows into or out of the system also changes
the entropy of the surroundings.
• For an isothermal process:

• At constant pressure, qsys is simply

H for the system.

Chemical
Thermodynamics
 Link S and H: Phase changes

A phase change is isothermal

(no change in T).

Entropysystem
For water:
Hfusion = 6 kJ/mol
Hvap = 41 kJ/mol
If we do this reversibly: Ssurr = –Ssys Chemical
Thermodynamics
 Standard Entropy

• Standard entropy: absolute entropy of a

substance at 1 atm (typically at 25C)
• Complete list in Appendix 2 of text
What do you notice about entropy values
for elements and compounds?
• Units: J/K·mol

Chemical
Thermodynamics
Entropies

Chemical
Thermodynamics
 Trends in Entropy

• Entropy for gas phase is greater than that of

liquid or solid of same substance
 I2 (g) has greater entropy than I2 (s)
• More complex structures have greater
entropy
 C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower
entropy
 Diamond has lower entropy than graphite
Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
• Ssolid < Sliquid

Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
• Sliquid < Svapor

Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
• Spure < Saqueous

Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
Slower temp < Shigher temp

Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
• Sfewer moles < Smore moles

Chemical
Thermodynamics
Entropy Changes in a System
Qualitative
Determine the sign of S for the following
(qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a
solid yellow precipitate forms
3. Liquid water is heated from 22.5
C to 55.8 C
Chemical
Thermodynamics
Entropy Changes in the System

Entropy can be calculated from the table

of standard values just as enthalpy
change was calculated.

Srxn = nS products  mS reactants

Chemical
Thermodynamics
 Standard Entropy

• Calculate the standard entropy change

for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2NH3(g)  N2(g) + 3H2(g)
nS products

Chemical
Thermodynamics
 Standard Entropy

2NH3(g)  N2(g) + 3H2(g)

Srxn = nS products  mS reactants

= [(1)(191.5 J/K · mol) + (3)(131.0 J/K · mol)]

- [(2)(193.0 J/K · mol)]
= 584.5 J/K · mol - 386 J/K · mol
Srxn = 198.5 J/K · mol (Entropy increases)
(2 mol gas  4 mol gas)
Chemical
Thermodynamics
 Your Turn!

• Calculate the standard entropy change

for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2H2(g) + O2(g)  2H2O (g)

Chemical
Thermodynamics
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
directly proportional to the enthalpy of
the system.
Ssurroundings   Hsystem

Notice: exothermic process corresponds

to positive entropy change in
surroundings
Chemical
Thermodynamics
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
inversely proportional to temperature
Ssurroundings  1 / T

Combining the two expressions:

Hsys
Ssurr 
T
Chemical
Thermodynamics
 Entropy Changes
If the entropy change for a system is
known to be 187.5 J/Kmol and the
enthalpy change for a system is known
to be 35.8 kJ/mol, is the reaction
spontaneous?
Spontaneous if: Suniv= Ssys + Ssurr > 0

Hsys
Ssurr 
T Chemical
Thermodynamics
 Entropy Changes

Is the reaction spontaneous?

35,800 J/mol
Ssys   120.0J/K  mol
298 K

Suniv= -187.5 + 120.0 < 0 so the reaction

is non-spontaneous
Chemical
Thermodynamics
Practical uses: surroundings & system
Entropy Change in the Universe
• The universe is composed of the system and
the surroundings.

Therefore,
Suniverse = Ssystem + Ssurroundings

• For spontaneous processes

Suniverse > 0
Chemical
Thermodynamics
Practical uses: surroundings & system

Chemical
= – Gibbs Free Energy Thermodynamics
Practical uses: surroundings & system

= – Gibbs Free Energy

Make this equation nicer:

Chemical
Thermodynamics
 Practical uses: surroundings & system
…Gibbs Free Energy
TSuniverse is defined as the Gibbs free
energy, G.

For spontaneous processes: Suniverse > 0

And therefore: G < 0

G is easier to determine than Suniverse.

So:
Chemical
Use G to decide if a process is spontaneous.
Thermodynamics
Gibbs Free Energy
1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system
is at equilibrium.
3. If G is positive, the
reaction is spontaneous
in the reverse direction.

Chemical
Thermodynamics
Standard Free Energy Changes
Standard free energies of formation, Gf
are analogous to standard enthalpies of
formation, Hf.

G can be looked up in tables,

or
calculated from S° and H.
Chemical
Thermodynamics
 Free Energy Changes

Very key equation:

This equation shows how G changes with

temperature.
(We assume S° & H° are independent of T.)
Chemical
Thermodynamics
Free Energy and Temperature

• There are two parts to the free energy

equation:
 H— the enthalpy term
 TS — the entropy term

• The temperature dependence of free

energy comes from the entropy term.
Chemical
Thermodynamics
 Free Energy and Temperature

By knowing the sign (+ or -) of S and H,

we can get the sign of G and determine if a
reaction is spontaneous.
Chemical
Thermodynamics
 Free Energy and Equilibrium
Remember from above:
If G is 0, the system is at equilibrium.

So G must be related to the equilibrium

constant, K (chapter 15). The standard free
energy, G°, is directly linked to Keq by:

Chemical
Thermodynamics
 Free Energy and Equilibrium
Under non-standard conditions, we need to use
G instead of G°.

Q is the reaction quotiant from chapter 15.

Note: at equilibrium: G = 0.
away from equil, sign of G tells which way rxn goes
Chemical
spontaneously. Thermodynamics
Gibbs Free Energy
1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system
is at equilibrium.
3. If G is positive, the
reaction is spontaneous
in the reverse direction.

Chemical
Thermodynamics
 Example

For a reaction in which H = 125 kJ/mol

and S = 325 J/Kmol, determine the
temperature in Celsius above which the
reaction is spontaneous.
H 125 kJ/mol
T    385 K
S 0.325 kJ/K×mol

385 K  273 = 112C

Chemical
Thermodynamics
Copyright McGraw-Hill 2009
Standard Free Energy Changes

Free energy can be calculated from the

table of standard values just as
enthalpy and entropy changes.

Grxn = nG products  mG reactants

Chemical
Thermodynamics
Copyright McGraw-Hill 2009
Standard Free Energy Changes

Calculate the standard free-energy

change for the following reaction.
2KClO3(s)  2KCl(s) + 3O2(g)
Grxn = nG products  mG reactants
= [2(408.3 kJ/mol) + 3(0)]  [2(289.9
kJ/mol)]
= 816.6  (579.8) = 236.8 kJ/mol
(spont) Chemical
Thermodynamics
 Free Energy and Chemical
Equilibrium
• Reactions are almost always in
something other than their standard
states.
• Free energy is needed to determine if a
reaction is spontaneous or not.
• How does free energy change with
changes in concentration?
Chemical
Thermodynamics
 Free Energy and Equilibrium

G = G° + RT ln Q
 G = non-standard free energy
 G° = standard free energy (from
tables)
• R = 8.314 J/K·mole
• T = temp in K
• Q = reaction quotient
Chemical
Thermodynamics
 Free Energy and Equilibrium

• Consider the reaction,

H2(g) + Cl2(g)  2 HCl(g)
How does the value of G change when
the pressures of the gases are altered
as follows at 25 C?
• H2 = 0.25 atm; Cl2 = 0.45 atm;
HCl = 0.30 atm
Chemical
Thermodynamics
 Free Energy and Equilibrium

First, calculate standard free energy:

H2(g) + Cl2(g)  2 HCl(g)
G° = [2(95.27 kJ/mol)]  [0 + 0] =
190.54 kJ/mol
Second, find Q: (P )2 2
HCl (0.30)
QP    0.80
(P ) ( P ) (0.25) (0.45)
H Cl
2 2
Chemical
Thermodynamics
Free Energy and Equilibrium

Solve: G = G° + RT ln Q
G = 190,540 J/mol + (8.314J/K·mol)
(298 K) ln (0.80)

G =  191.09 kJ/mol (the reaction

becomes more spontaneous - free
energy is more negative)
Chemical
Thermodynamics
 Your Turn!

• Consider the reaction,

O2(g) + 2CO(g)  2CO2(g)
How does the value of G change when
the pressures of the gases are altered
as follows at 25 C?
• O2 = 0.50 atm; CO = 0.30 atm;
CO2 = 0.45 atm
Chemical
Thermodynamics
Relationship Between G° and K

• At equilibrium, G = 0 and Q = K
• The equation becomes:
0 = G° + RT ln K
or
G° = – RT ln K

Chemical
Thermodynamics
Relationship Between G° and K

Chemical
Thermodynamics
Relationship Between G° and K

• Using the table of standard free

energies, calculate the equilibrium
constant, KP, for the following reaction
at 25 C.
2HCl(g) H2(g) + Cl2(g)

Chemical
Thermodynamics
Relationship Between G° and K

First, calculate the G°:

= [0 + 0]  [2(95.27 kJ/mol)]
= 190.54 kJ/mol (non-spontaneous)
Substitute into equation:
190.54 kJ/mol =  (8.314 x 103 kJ/K·mol)(298 K)
ln KP
76.90 = ln KP = 3.98 x 1034
K < 1 reactants are favored Chemical
Thermodynamics
 Your Turn!

• Calculate the value of the equilibrium

constant, KP, for the following reaction
at 25 C.
2NO2(g) N2O4(g)

Chemical
Thermodynamics
18.6 Thermodynamics in Living
Systems
• Coupled reactions
• Thermodynamically favorable reactions
drives an unfavorable one
• Enzymes facilitate many
nonspontaneous reactions

Chemical
Thermodynamics
Thermodynamics in Living Systems

• Examples:
C6H12O6 oxidation: G° = 2880 kJ/mol
ADP  ATP G° = 31 kJ/mol
Synthesis of proteins: (first step)
alanine + glycine  alanylglycine
G° = 29 kJ/mol
Chemical
Thermodynamics
Thermodynamics in Living Systems

• Consider the coupling of two reactions:

ATP + H2O + alanine + glycine  ADP +
H3PO4 + alanylglycine
Overall free energy change:
G° = 31 kJ/mol + 29 kJ/mol = 2 kJ/mol
Protein synthesis is now favored.
Chemical
Thermodynamics
ATP-ADP Interconversions

Chemical
Thermodynamics
 Key Points

• Spontaneous vs nonspontaneous
• Relate enthalpy, entropy and free
energy
• Entropy
Predict qualitatively
Calculate from table of standard values
Calculate entropy for universe
Chemical
Thermodynamics
 Key Points

• Free energy
Calculate from table of standard values
Calculate from Gibbs equation
Calculate non-standard conditions
Calculate in relationship to equilibrium
constant

Chemical
Thermodynamics