CHEMICAL

THERMODYNA
MICS
Chapter
19

1
 Stoichiometry predicts “how much” for complete

(irreversible) reactions.
 Equilibrium predicts “how much” for
(reversible) equilibrium reactions.

 Kinetics predicts “how fast”

 Thermodynamics predicts “how possible (& the

extent)” a reaction is under a given set of conditions.

2
Thermodynamic
s is the study of
energy
transformation.

3
19.1: Spontaneous Processes
Recall: First Law of Thermodynamics:
• energy cannot be created nor destroyed.
(The total energy of the universe is a constant.)
• However, energy can be converted from one form to
another or transferred from a system to the
surroundings or vice versa.
Work done on (or by) the
Change in internal ∆E = q + w system.
energy
Heat exchanged between the
system and the surroundings
4
Spontaneous Processes

• 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 follow the
reverse process.

5
Some spontaneous processes:

- A waterfall runs downhill, but never up

- A lump of sugar dissolves in a cup of coffee, but dissolved

sugar does not spontaneously reappear in its original form.

- Heat flows from a hotter object to a colder one, but the

reverse never happens spontaneously.

- A piece of Na reacts violently with water to form NaOH and H2,

but the reverse doesn’t happen.

- Iron exposed to water and oxygen forms rust, but rust does
not spontaneously change back to iron.

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Processes that are spontaneous
in one direction are non-
spontaneous in the reverse
direction.

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 Also, processes that are spontaneous at one
temperature may be non-spontaneous at other
temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.

8
Some spontaneous processes are exothermic,
while others are endothermic.

Exothermicity favours spontaneity, but does not guarantee it.

Other thermodynamic properties needs to be considered.

Why? Lower energy states tend to be more stable than

higher energy states, and exothermic changes result in the
system achieving a lower energy state.

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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.
(no net change to the system or
surroundings)

Changes are infinitesimally

small in a reversible process.

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 Irreversible Processes

• Irreversible processes cannot simply be reversed to restore the

system and surroundings to their original states. Gas expands
(no work done on surroundings, but pushing piston back in,
requires work)
• All spontaneous processes are irreversible .
(the nonspont. reversible reaction requires work to be done –
surroundings have changed).

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19.2: Entropy and the Second Law of Thermodynamics

• Entropy (S) is a term coined by Rudolph Clausius in the

19th century.

Entropy can be thought of as

 a measure of the
randomness (disorder) of a
system

OR (better)
 the extent to which energy is distributed or dispersed
among the various motions of molecules of the system.

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A system (such as a room) is in a state of high entropy when its
degree of disorder is high.

For better or for worse,

nature 'likes' chaos,
disorder, high entropy...

In fact, much of our life

consists in fighting this
disorder!

13
Entropy can be explained in terms of probabilities.

Disordered states are simply more likely to exist (or emerge) than
ordered states.

The spontaneous direction of change is from a less probable to a

more probable state, as illustrated above.
You can’t un-shuffle a deck of cards.
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 c es s es
e se p ro se
Th n inc r ea
to a
lead y o f t he
n t ro p
in e
s te m :
sy

15
 For different substances in the same phase, the molecular
complexity and molar mass determine which ones have
higher entropy values.

He(g) vs. Ne(g)

So = 126.1 J/K mol So= 146.2 J/K mol

So = 2.44 J/K mol So = 5.69 J/K mol

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17
18
Which has higher entropy?
– Solid CO2 or gaseous CO2?
– N2 gas at 1 atm or N2 gas at 0.01 atm?

Will entropy increase or decrease?

– Solid sugar is added to water
↑ because larger volume
– Iodine vapor condenses on cold surface to form
crystals
↓ because gs

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 Entropy Change
• Like total energy, E, and enthalpy, H, entropy is a
state function [a property of a system that is
determined by the state of a system (T, P, V, [ ], etc.)
regardless of how that condition was achieved].
Ex. The state of a gas is specified by its V, P and T.

• The change in entropy depends only on the

initial and final states of the system,

S = Sfinal  Sinitial

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For a process occurring at constant temperature (an
isothermal process): (like phase changes)

Entropy
in J/K Hfus, Hvap

heat is transferred when the process

is carried out reversibly at a constant
temperature.

T = temperature in Kelvin.

If a change between 2 states is irreversible, calculate ∆S using a

reversible path between the states.

21
For example :
Calculate entropy change when 36.0 g of ice melts
at 273 K and 1 atm.
(the enthalpy of fusion for ice = 6.01 kJ/mol)

n = (36 g)/(18 g mol-1) = 2.0 mol

∆Sfusion = (2.0 mol)(6.01 kJ mol-1) / 273 K

= 0.0440 kJ / K = 44.0 J/K

22
For example:
The element mercury is a silvery liquid at room
temperature. The normal freezing point of mercury is
-38.9oC, and its molar enthalpy of fusion is ∆Hfus = 2.29
kJ/mol. What is the entropy change of the system
when 50.0 g of mercury freezes at the normal freezing
point?
=(mol)(q) = (50.0 g)(200.59g/mol)(-2.29 kJ/mol)
T (-38.9 + 273)

= -0.571 kJ = -0.00244 kJ/K

234.1 K
= - 2.44 kJ/K
For any reaction event we can refer to the reaction system: ∆Ssys
and the surroundings: ∆Ssurr

Logically: ∆Suniv = ∆Ssys + ∆Ssurr

If we can calculate ∆Suniv for a given reaction system, then:

i) If ∆Suniv = positive, then the reaction is spontaneous in

the direction written.

ii) If ∆Suniv = negative, then the reaction is non-spontaneous

in the direction written, but would be
spontaneous in the opposite direction.

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 Second Law of Thermodynamics
The entropy of the universe:
does not change for reversible (equilibrium) processes:
Reversible (ideal):
(slow isothermal compression or expansion of a gas, phase change (melting))

and *increases for spontaneous processes.

Irreversible (real, spontaneous):
(dissolving a salt, diffusion, ..)

But, entropy can decrease for individual systems.

If <<
Reaction is spontaneous in reverse

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H2O(l)  H2O(g)

∆Ssys has a positive sign due to the increase in # of

positions (liquid to gas)

∆Ssurr is determined mostly by heat flow

Vaporization is endothermic so it removes heat from the

surroundings, which decreases random motion of
surroundings……Negative ∆Ssurr

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 Determining ∆Ssurr
Sign of ∆Ssurr
• depends on direction of heat flow
• ∆Ssurr is + for exothermic reactions
• ∆S
surr is - for endothermic reactions
Magnitude of ∆Ssurr
• Depends on temperature
• Heat flow = ∆H at constant P
• Very small at high T, increases as T decreases

H rxn
S surr 
T
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 Temperature’s Effects
• If the ∆Ssys and ∆Ssurr have different signs, the
temperature determines the ∆Suniv
H2O(l)  H2O(g)
• For vaporization (boiling) of water
– Above 100°C, ∆Suniv is positive
– At 100oC, ∆Suniv is zero
– Below 100°C, ∆Suniv is negative

• Impact of the transfer of heat will be greater

at lower temperatures
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 For example: Determine the entropy change that occurs
when an ice cube melts in your hand (body temp. = 37oC):
(assume that a mole of ice is melting, Hfus = 6.01 x 103 J/mol))
∆Suniverse = ∆Ssys + ∆Ssurr System? Surroundings?

Ice melting:
∆Ssystem = qrev = (1 mol)(6.01x103 J/mol) = 22.0 J/K
(heat gained by 273 K
ice) T

(heat lost by ∆Ssurroundings = qrev = (1 mol)(-6.01x103 J/mol) = -19.4 J/K

surroundings) T
310 K
∆Suniverse = ∆Ssys + ∆Ssurr = 22.0 +(-19.4) = + 2.6 J/K

Therefore, for the spontaneous process of

ice melting, entropy increases.
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Summary (memorize)

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32
33
19.3: The Molecular Interpretation of Entropy
• 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.
• Molecules exhibit several types of motion:
– Translational: Movement of the 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.

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• Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.

• He referred to this sampling as a microstate of the

thermodynamic system.

• 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.

35
 S = k lnW
Here is a simple system of
4 molecules.
Distribution:

There are 11 possible

ways to distribute them
within 2 compartments.
These are called
“microstates”.

Distribution 1 is least
probable, and 3 is most
probable.

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The number of microstates (and therefore the entropy)
tends to increase with increases in:
– Temperature

– Volume (gases)

– The number of independently moving

molecules (S(g) > S(l) > S(s))

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Solutions Dissolution of a solid:
Ions have more entropy than the
crystal lattice (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 make a lot of
water molecules align around them.)

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Entropy Changes during chemical reactions:
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. 2 NO(g) + O2(g) → 2NO2(g)
In this example the entropy
decreases. More atoms are held in
bonds and there are less molecules
overall.
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Third Law of Thermodynamics
The entropy of a pure crystalline substance
at absolute zero is 0.

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Entropy increases as the temperature of a
crystalline solid is increased from absolute zero.

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 19.4: Entropy Changes in Chemical Reactions
Standard Entropies (So)
• These are molar entropy values of
substances in their standard states.

• Standard entropies tend to increase

with increasing molar mass.

• Larger and more complex molecules

have greater entropies.

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Entropy Changes
Entropy changes for a reaction can be calculated the
same way we calculated H:

∆Srxn = ∑So products - ∑So reactants

S° for each component is found in a table.

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 Example;
Using Table 19.2, calculate the change in entropy for the
formation of ammonia from hydrogen gas and nitrogen gas
(at 298 K).
N2(g) + 3H2(g) → 2NH3(g)

∆Ssys = ∑So products - ∑Soreactants

= [2SoNH3(g) ]- [SoN2(g) + 3SoH2(g)]
= [(2 mol)(192.5 J/mol K)]- [(1 mol)(191.5 J/mol K) + (3 mol)(130.6 J/mol K)]

∆Ssys = -198.3 J/K

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Be sure to Watch Units
read the – entropy in
correct J not kJ.
column!

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 Example:
Find the ∆S° at 25°C for:
2NiS(s) + 3O2(g)  2SO2(g) + 2NiO(s)
So 53 205 248 38

∆Ssys = ∑So products - ∑Soreactants

= [2SoSO2(g) + 2SoNiO]- [2SoNiS(g) + 3SoO2(g)]

= [2(248) + 2(38)]- [2(53) + 3(205)]

= - 149 J/K

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Entropy Changes in Surroundings:
Recall: sys
• Heat that flows into or out of the system also
changes the entropy of the surroundings.
So, for an isothermal process:

• At constant pressure, qsys is simply Hf

(standard heat of formation) for the system.

Recall: Hf = ∑ Hfproducts - ∑ Hf reactants

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 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

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Example;
Calculate the change in entropy (surrounding) for the
formation of ammonia from hydrogen and nitrogen at 298 K,
using standard heats of formation.

N2(g) + 3H2(g) → 2NH3(g)

∆Ssurr = -[∑Hfo products - ∑Hforeactants]

T
∆ Hfo = [2HfoNH3(g) ]- [HfoN2(g) + 3HfoH2(g)]

∆ Hfo = [(2 mol)(-46.19k J)]- [(1 mol)(0 kJ) + (3 mol)(0 kJ)]

∆Ssurr = -[-92.38 kJ] = 310 J/K

298 K
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Entropy Change in the Universe

Recall:

The universe is composed of the system and the surroundings.

Therefore,
Suniverse = Ssystem + Ssurroundings

For spontaneous processes

Suniverse > 0

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Note – for a system of nitrogen gas, hydrogen gas,
and ammonia:

∆Ssys = ∑So products - ∑Soreactants = -198.3 J/K

∆Ssurr = -[∑Hfo products - ∑Hforeactants] = 310 J/K

T
∆Ssurr > ∆Ssys

∆Suniv = (-198.3 J/K + 310 J/K) = 112 J/K

Since ∆S is positive – reaction is spontaneous.

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Some reactions are spontaneous because they give off
energy in the form of heat (∆H<0).

Others are spontaneous because they lead to an

increase in entropy of the system (∆S > 0).

Favorable Unfavorable
Ho < 0 Ho > 0
So > 0 So < 0

Calculations of ∆H and ∆S can be used to probe the

driving force behind a particular reaction.

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But what happens when one of the potential driving
forces behind a chemical reaction is favorable and the
other is not?

We can answer this by using Gibbs Free Energy (G),

which reflects the balance between these two forces.

This quantity is the energy associated with a chemical

reaction that can be used to do work.

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19.5: Gibbs Free Energy
J. Willard Gibbs developed a way to determine whether a
reaction occurring at constant temperature and pressure would
be spontaneous, using just ∆H and ∆S.

Two Factors affecting spontaneity:

1) Tendency to go to a lower enthalpy.

(exothermic)

2) Tendency to go to a higher entropy.

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 Recall that for a reaction occurring at constant T and P:

and

Multiplying both sides by -T and rearranging gives:

Gibbs Free
Energy temperature
(K)

To Remember: Get home to supper! 55

 For spontaneous processes: Suniverse > 0
And therefore: G < 0
G is easier to determine than Suniverse.
So use G to decide if a process is spontaneous.

1. If DG is negative, the forward reaction is spontaneous.

(moving forward to get to equil.)

2. If DG is 0, the system is at equilibrium. No net change.

(allows us to calculate K)

3. If G is positive, the reaction is spontaneous in the reverse

direction. (moving backwards to get to equil.)

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Gibbs Free Energy

57
 Example:
+∆H: endothermic +∆S: increasing chaos
H2O(s)  H2O(l)
(where ∆H°=6.03x103 J/mol and ∆S°sys=22.1 J/mol.K)
At -10°C, is this reaction spontaneous?

∆G = (6.03 x 103 J/mol) – (263 K) (22.1 J/mol K)

∆G = 2.2 x 102 J/mol

∆G = positive

NO!- the reverse is spontaneous

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Same Example:

What could be another way to check for spontaneity?

Check to see if the ∆Suniv is positive.

How can we solve for ∆Ssurr? use ∆H° and T

∆Suniverse = ∆Ssys + ∆Ssurr

∆Ssurr = -q = -6.03 x103 J/mol = -22.9 J/mol K

T 263 K
∆Suniv = - 22.9 J + 22.1 = - 0.8 J/mol K

NO!- the reverse is spontaneous

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Example
Is it spontaneous at 0°C?

∆G = (6.03 x 103 J/mol) – (273 K) (22.1 J/mol K)

∆G = 0
NO!- it is at equilibrium so no shift

OR: 6.03  103 J/mol

Ssurr    22.1J / molK
273K

Suniv  22.1  22.1  0 J/molK

NO! It is at equilibrium so no shift

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 Example:
At what T is the following reaction spontaneous at 1 atm?
Br2(l)  Br2(g) (∆Ho=31.0 kJ/mol, ∆S=93.0 J/molK
+∆S: increasing
Looking for boiling point: ∆G=0 chaos
+∆H: endothermic

0 = (3.1 x 104 J/mol) – (T in K) (93 J/mol K)

-(3.1 x 104 J/mol) = – (T in K) (93 J/mol K)

T=333K: boiling pt.
T>333K: spontaneous
T<333K: reverse is spont
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 Free Energy and Temperature

Enthalpy Entropy
term term

The temperature dependence of free energy comes

from the entropy term.

62
 ∆H ∆S Spontaneous?
endothermic + + at higher temperatures
exothermic - - at lower temperatures
- + at all temperatures
+ - never

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

we can get the sign of G and determine if a
reaction is spontaneous.

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What does Spontaneous or Nonspontaneous Mean?

1) Physical change – if spontaneous, it goes to completion

(100% change). (an ice cube doesn’t stop melting at 10oC)

2) Chemical reaction: spontaneous means a reaction will

give more products. The reaction may reach equilibrium,
but K>1.

Nonspontaneous does not mean “no reaction”. It means

that reactants are favored (K<1)

Nonspontaneous reactions can be made to occur by use of

an outside energy source (e.g. electrolysis of water)

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65
 Very important!

Note – where the signs for enthalpy and entropy are the
same, results are temperature dependent.

- Where signs are opposite, results are NOT temp. dependent

66
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.

The more negative ∆G° is, the further a reaction’s

equilibrium position lies to the right
67
Use standard free energy data to determine the free energy
change for each of the following reactions, which are run under
standard state conditions:

a) MnO2(s)→ Mn(s) + O2(g)

b) H2(g) + Br2(l) → 2HBr(g)

68
The concept of Hess's law of heat summation can be
expanded to include changes in entropy and in Gibbs
Free Energy.
Use the following data at 25oC to calculate ∆Go for
the reaction: Cdiamond → Cgraphite
Cdiamond + O2(g) → CO2(g) ∆Go = -397 kJ
Cgraphite + O2(g) → CO2(g) ∆Go = -394 kJ

Cdiamond + O2(g) → CO2(g) ∆Go = -397 kJ

CO2(g) → Cgraphite + O2(g) ∆Go = +394 kJ
Cdiamond → Cgraphite

Flip the second equation, therefore ∆Go = +394 kJ

∆Go = -397 kJ + 394 kJ = -3.00 kJ

69
Free Energy and Equilibrium
Remember:
If DG is 0, the system is at equilibrium.
So DG must be related to the equilibrium constant, K .

The standard free energy, DG°, is directly linked to

Keq by:

R = 8.314 J/mol K, T in Kelvin

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Looking at N2(g) + 3H2(g) → 2NH3(g):
1) ∆Go simply tells us how much free energy change would occur if reactants
(N2 and H2) in their standard states (diatomic gases) are completely
converted to products (NH3) in their standard states (g).

Possible outcomes:
a) ∆Go = negative, (i.e. -33.3 kJ) This gives us the maximum amount of
work that would be done by the system on its surroundings if 1 mol of N2
and 3 mol of H2 are completely converted to 2 mol of NH3.

b) ∆Go = positive. This gives us the amount of work that the surroundings
would have to do on the system.

c) ∆Go = zero. This tells us that the products and reactants have exactly the
same amount of free energy.

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2a) Value for ∆Go can be calculated using:

∆Gorxn = ∑n∆Goprod - ∑∆Goreact Or ∆Go = ∆Ho – T∆So

b) In either case, for the nitrogen and hydrogen reaction,

we get -33.33 KJ. For equilibrium situations, we will never
get this much work out of the system, since the reaction
will not go forward to completion. Nevertheless, the
magnitude and sign of ∆Go gives us valuable information.

GR
free energy -33.33 kJ (if fully reacts)
GP

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c) When we introduce reactants and/or products into the
reaction vessel, the reaction could proceed toward
equilibrium in either direction (forward or reverse).

It should be obvious that any system will go forward (right)

to equilibrium if we exclusively introduce reactants at t=0,
just as any system will proceed in reverse (left) if we
exclusively introduce products at t=0)

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d) The sign and magnitude of ∆Go provide some assistance in
this context. Here is what it does for us:

∆Go sign ∆Go magnitude Comments K value

Large Equil. position lies far
negative to the right →→ K>1

Small Equil. position lies to

the right →

Large Equil. lies far to the

positive left ←← K<1

Small Equil. lies to the left

←

zero - middle K=1

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3) When systems reach equilibrium, the following is true:

a) The total system free energy is at a minimum

b) The free energy of reactants = free energy of products.

4) The magnitude and sign of ∆Go are helpful, but the

following equation is even more useful, as it allows us to
determine, at any instant in time, which way the system
will move to get to equilibrium.

75
Under non-standard conditions, we need to use DG
instead of DG°.

standard K = At equilibrium

Non- Q = not at
standard equilibrium

Q is the reaction quotient from equilibrium.

Note: - at equilibrium: DG = 0.
- away from equil, sign of DG tells which way reaction
goes spontaneously.

76
Simple Reminders and Rules for Interpreting and Using G:

a) ∆Go is standard free energy change and it simply suggests

whether equilibrium lies to the right or left.

b) If ∆G is a negative value – the system must still be moving

forward to get to equilibrium. (This could be true for – or
+ ∆Go values)

c) If ∆G is a positive value – the system must still be moving

reverse to get to equilibrium. (This could be true for – or +
∆Go values)

d) Once equilibrium is reached ∆G becomes 0. This allows us

to calculate the equilibrium constant Kp.

77
Example: N2(g) + 3H2(g)  2NH3(g)

For the reaction above, ∆G° =-33.3 kJ/mol. For each of the
mixtures below at 25°C, predict the direction in which the
system will shift to reach equilibrium.
a) pNH3 = 1.00 atm, PN2 = 1.47, PH2 = 0.0100
( p NH 3 ) 2 (1.00) 2
Q   6. 80  10 5

( p N 2 )( p H 2 ) 3 (1.47)(. 0100) 3

∆G = (-3.33x104J) + (8.314J/mol K))(298)(ln6.80x105)

∆G=0 already at equilibrium- no shift

78
b) pNH3 = 1.00 atm, PN2 = 1.00, PH2 = 1.00

( p NH 3 ) 2 (1.00) 2
Q 3
 3
 1.00
( p N 2 )( p H 2 ) (1.00)(1.00)

∆G = (-3.33x104J) + (8.314)(298)(ln 1.00)

∆G= (-3.33x104J) + 0 = -3.33x104J

Since ∆G is negative, system needs to create more products,

shifts right.

79
 Another Example:
Find the ∆G for the following reaction at 25°C, with CO at 5.0 atm
and H2 at 3.0 atm.
CO(g) + 2H2(g)  CH3OH(l)
-137kJ/mol 0 -166kJ/mol
• must find ∆G° first (values from appendix are shown)
∆G°= -166 - [-137 + (2x0)] = -29 kJ = -29000 J

• calculate Q from pressure Q  1 1 2

  2 .2  10
( pCO )( pH 2 ) 2 (5.0)(3.0) 2

∆G= (-2.9x104 J) + (8.314)(298K)(ln2.2x10-2)

∆G = -3.8x104 J = -38 kJ/mol
80
When hydrogen iodide gas is produced from its gaseous elements
at 25.OoC, ∆Go = 3.30 kJ/mol. Find the value of Kp at this
temperature.

At equilibrium, ∆G = 0, therefore

3300 J/mol = - (8.314)(25+273)(lnK)

K = 0.264

81
Indicate whether the equilibrium position lies to the left
or the right and give the general size of the equilibrium
constant, K:

i) A reaction has a ∆H = + and ∆S = -

∆Go = +, therefore position lies to the left (K<1)

ii) Gaseous butene (C4H8) reacts with oxygen to produce

carbon dioxide and water vapour.

∆Ho = - (exo) ∆So = + (gas production) therefore

∆Go = -. Position lies to the right (K>1)

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That’s it for Chapter 19.

Time for practice.

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