thermodynamics: the study of energy and

its transformations
-- thermochemistry: the subdiscipline of
thermodynamics involving
chemical reactions and
energy changes
 Energy
Energy is defined as the
capacity to do work.

Units of energy are (among others)

joules (J),
kilojoules (kJ), SI unit James
calories (cal), or Prescott
nutritional calories (Cal or kcal). Joule
(1818-1889)
-- conversions:
4184 J = 4.184 kJ = 1000 cal = 1 Cal = 1 kcal

1 nutritional calorie
-- Energy moves whenever…(1) work is done
...or (2) heat is transferred

Work (w) is done when

a force moves through
a distance. w = F d
ME BY _____.
If you push me, work is done ON _____ YOU
YOU
Energy is transferred from _____ ME
to _____.
Heat (q) is an amount of
energy transferred from a
hotter object to a colder one.
If you fall face-first into the snow,
your face to ________.
energy is transferred from ________ the snow
SUMMARY: Introduction to Energy
Thermodynamics is the scientific study of energy and
its transformations; thermochemistry is the branch
of this that deals with energy in chemical reactions.
Energy is the capacity to do work. The SI unit for
energy is the joule (J).
Energy moves whenever work (w) is done, OR
whenever heat (q) is transferred between objects
of differing temperature. When work is done, the
object DOING the work loses energy; the one
having work done ON it gains energy. When heat is
transferred, the warmer object loses energy; the
cooler object gains energy.
 kinetic energy: energy of motion
m in kg; v in m/s;
KE = ½ mv 2
for KE in J
-- All masses have KE.
In chemistry, we are
most interested in the
kinetic energy of...
tiny particles (e.g.,
atoms and molecules).
-- Thermal energy is due
to the KE of tiny particles.
We measure the average KE of a
collection of particles as... temperature.
Find the kinetic energy of a
single dinitrogen monoxide
molecule moving at 650 m/s.
N2O (laughing gas)

KE = ½ mv2

?
 1g   1 kg 
m = 44 amu  23  
 6.02 x 10 amu   1000 g 
= 7.31 x 10–26 kg
KE = ½ (7.31 x 10–26 kg) (650 m/s)2
= 1.5 x 10–20 J
potential energy: stored energy ––––
Chemical potential energy + –– +
– –
electrostatic forces
is due to... –
between charged particles. d of PEmin

-- related to the specific

arrangement of
Mg2+ O2–
atoms and
electrons in
the substance

Mg2+ S2–
SUMMARY: Kinetic and Potential Energy
Kinetic energy is energy of motion. In
chemistry, we are most interested in the
motion of atoms and molecules, rather than
that of macroscopic objects. Our measure of
the average kinetic energy of a collection of
particles is the collection’s temperature.
Potential energy is stored energy. In chemistry,
we are most interested in the energy stored
in the chemical bonds and intermolecular
forces between particles. This PE is related
to the identity of the particles in question and
their spatial relation to one another.
 Review: Kinetic & Potential Energy
Kinetic energy is energy of motion. All tiny
chemical particles are – in some way – in
motion; thus, all have SOME amount of KE.
The average KE of a collection of particles is
its temperature.

Potential energy is stored energy. The PE

between chemical particles is related to the
forces between them, which is based on the
identity of the particles and their spatial
relation to each other.
 system: the part of the universe we are studying
at some particular time
surroundings: everything else
-- In chemistry, a system can
exchange energy
______ but not
matter with its surroundings.
______

Some (mostly-good) examples of chemical systems.

internal energy (E) of a system: the sum of all the
KE and PE of the components of a system
(this can be a challenge to quantify)

-- The change in the internal energy

of a system would be found by: DE = Efinal – Einitial
And for chemistry, this equation would become:
DE = Eproducts – Ereactants

DE is + if E>final Einitial (i.e., system...gains energy

)
 ENDERGONIC
DE is – if E<final Einitial (i.e., system...loses energy
)
 EXERGONIC
Short detour: Endergonic / Exergonic /
Endothermic / Exothermic

endergonic: energy goes IN...PERIOD.

endothermic: energy goes IN...in the form of HEAT.
endothermic processes are
Thus, all ___________
___________,
endergonicbut NOT all
___________
endergonicprocesses are
endothermic
___________.
phase changes: e.g., melting
endergonic boiling photosynthesis:
AND sublimation endergonic,
endothermic but NOT
In ‘end-,’ internal energy... increases. endothermic
Short detour: Endergonic / Exergonic /
Endothermic / Exothermic
(CONT.)

exergonic: energy comes OUT... PERIOD.

exothermic: energy comes OUT...in the form of HEAT.
exothermic processes are
Thus, all ___________
___________
exergonicbut NOT all
___________
exergonicprocesses are
exothermic
___________.
phase changes: e.g., freezing
chemi-
exergonic condensation
luminescence:
AND deposition exergonic ,
exothermic but NOT
In ‘ex-,’ internal energy... decreases. exothermic
The most efficient way to find the
change in a system’s internal
energy DE is by finding two rather-
easily measured quantities:
q: the heat transferred
w: the work done

DE = q + w

– system RELEASED heat.

If q is ___,
Sign
conventions
+ system ABSORBED heat.
If q is ___, are from the
– system DID work.
If w is ___, system’s
point of
+ system had work done ON it.
If w is ___, view.
In sum...Internal Energy and Its Changes
(2-for-one...) In endergonic / EXERGONIC
processes, energy is absorbed / RELEASED by
a system; if the energy is HEAT, we could be
more specific and call it an endothermic /
EXOTHERMIC process.
It is NOT easy to determine the absolute value
of a system’s internal energy E. It is much easier
to find the change in internal energy DE, by
measuring the heat transferred (q) and the work
done (w). The +/– signs of q and w are taken
from the system’s point of view.
DE = q + w
 Enthalpy (H)

-- Enthalpy (H) is defined as... H = E + PV

where E = system’s internal energy
P = pressure of the system
V = volume of the system

The Dutch physicist and Nobel laureate

H.K. Onnes coined the term enthalpy,
Heike Kamerlingh Onnes basing it on the Greek term enthalpein,
1853–1926 which means “to warm.”
 -- There is much that could be said about
enthalpy, but what you need to know is:
If a process occurs at constant
pressure...
the change in enthalpy (DH) of the system
equals the heat (q) lost or gained by the
system.
i.e., DH = Hfinal – Hinitial = qP

P indicates constant pressure conditions.

When DH is +, the system... has gained heat. (ENDO)
When DH is –, the system... has lost heat. (EXO)
Enthalpy is an extensive property, meaning that…
the amount of material affects its value.
 In the burning of firewood at constant pressure, the
enthalpy change equals the heat released. DH is (–)
and depends on the quantity of wood burned.
DH for a reaction and its reverse Enthalpy/energy
are the opposites of each other. is a reactant.

2 H2(g) + O2(g) 2 H2O(g) (DH = –483.6 kJ)

(q is released)
2 H2O(g) 2 H2(g) + O2(g)(DH = +483.6 kJ )
(q is absorbed)

Enthalpy change depends

on the states of reactants
and products.

2 H2(g) + O2(g) 2 H2O(g) (DH = –483.6 kJ)

2 H2(g) + O2(g) 2 H2O(l) (DH = –571.6 )kJ
SUMMARY: Enthalpy, Conceptual
For processes that occur at constant
pressure, the change in enthalpy DH equals
the heat transferred (q). DH is (+) for
endothermic processes and (–) for
exothermic processes.
For a given reaction and its reverse, their
DHs have opposite signs. Also, the change
in enthalpy DH depends not only on the
substances in the reaction, but also on
their states of matter.
 REVIEW: Enthalpy
For processes that occur at constant
pressure, the change in enthalpy DH
equals the heat transferred (q). DH is (+)
for endothermic processes and (–) for
exothermic processes. The change in
enthalpy for a reaction depends on the
substances in the reaction and their
states of matter.
An enthalpy of formation (DHf) is the enthalpy change
associated with the formation of a substance.
-- also called… heat of formation (units are kJ/mol
or the equivalent)
If we say “standard” something, it means (for one
thing) that the temperature is _____.
25oC Also, we write the
something with... a naught symbol as a superscript: o.
e.g., standard enthalpy of formation is... DHfo.
-- DHfo for the most stable form of an element is
ZERO, e.g., DHfo for O2(g) or Al(s) or S8(s) = 0.
DHfo for O3(g) (or ANY compound) = 0.

STOP “Look ‘em UP, dude!”

 REVIEW: Enthalpy
For processes that occur at constant
pressure, the change in enthalpy DH
equals the heat transferred (q). DH is (+)
for endothermic processes and (–) for
exothermic processes. The change in
enthalpy for a reaction depends on the
substances in the reaction and their
states of matter.
 Consider the dissolution of a
chunk of the generic ionic MN2  M2+ + 2 N–
compound MN2 in water:
There are three enthalpy components that together
make up the DH of the solution process:
1. The solvent m’cules pull
DH1 is (+) the ions out of the lattice.
2. The solvent m’cules separate to
make space so there is room for
DH2 is (+) a ‘surrounded ion’ to fit in.
3. IMFs btwn solvent m’cules and
ions cause ions to ‘nestle in,’
DH3 is (–) w/solvent m’cules all around.
The relative magnitude of these three enthalpy STOP

components determines the overall DH of the

solution process... and, obviously, its sign (+ or –).
Heats of solution for many solids in aqueous have
been tabulated and are easily accessed.

Common Heats of Solution

substance kJ/mol
NH4NO3 25.69
NaOH –44.51
KOH –57.61
HNO3 –33.28
HCl –74.84
NH4Cl 14.78
 REVIEW: Enthalpy
For processes that occur at constant
pressure, the change in enthalpy DH
equals the heat transferred (q). DH is (+)
for endothermic processes and (–) for
exothermic processes. The change in
enthalpy for a reaction depends on the
substances in the reaction and their
states of matter.
For a reaction, the change in enthalpy DH – sometimes
heat of reaction – is for
reaction enthalpy or _____________
called _______________
the number of moles of reactants and products shown
by the coefficients in the equation.
2 H2(g) + O2(g) 2 H2O(g) (DH = –483.6 kJ)
The proportions shown in the equation are used in...
STOICHIOMETRY.

ENTHALPY

SUBSTANCE “A” SUBSTANCE “B”

CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) DH = –891 kJ

What is the change in enthalpy

E when 54 g methane are burned?
CH4

54 g CH4
( 1 mol CH4
16 g CH4 )( –891 kJ
1 mol CH4 ) = –3.0 x 103 kJ

What mass of water is made if

10,540 kJ are released? E
H2O

– 10,540 kJ
( 2 mol H2O
–891 kJ )( 18 g H2O
1 mol H2O ) = 425.9 g H2O
STOP
REVIEW: Enthalpy of Formation
An enthalpy of formation DHf (or heat of formation) is
the enthalpy change associated with the formation of
a substance. The standard enthalpy of formation is
specifically at a temp of 25oC and is represented DHfo.

The DHfo for the most common form of any element is

zero. The DHfo is NOT ZERO for compounds or for
less-common forms of elements (such as ozone, O3),
and THESE DHfos have been tabulated; we simply
look them up (or Google them).
 Earlier, we used the equation:
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) DH = –891 kJ
Where did THIS
come from? Experiment. That’s it.
-- But...we can roughly estimate any heat of reaction
using the DHfo of all Rs and Ps in the reaction:

DHorxn = Sn DHfo(products) – Sm DHfo(reactants)

where n and m are

the coefficients
in the balanced equation.
In short: P–R
Approximate the enthalpy change for the combustion
of one mole of methane. (ans. = –891 kJ)
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)
(Look the other DHfos up!)
–74.7 kJ/mol 0 kJ/mol –393.5 kJ/mol –241.8 kJ/mol
X1 X1 X2

–74.7 kJ –877.1 kJ
DHorxn = P–R
= –877.1 kJ – (–74.7 kJ)

= –802 kJ (~10% diff.)

Predict the equilibrium shifts and the changes in K
with temperature for... (Look these up!)

HEAT + 2 POCl3(g) 2 PCl3(g) + O2(g)

DHfo (kJ/mol) –542.2 –288.1 0
Strategy: 1) Use DHfos to estimate DHrxn.
2) Use Le Chat. to predict shifts.

DHrxn = P – R = 2(–288.1) – 2(–542.2)

= +508.2 kJ (endothermic)

as T ... shift ,K
as T ... shift ,K
STOP
 Calorimetry: the measurement of heat flow

-- device used is called energy in transit from a

a... calorimeter hotter to a colder object

heat capacity of an object: amount of heat needed to

raise object’s temp. 1 K (or 1oC)
molar heat capacity: amt. of heat needed to raise
temp. of 1 ____ mol
of a substance 1 K
specific heat (capacity): amt. of heat needed to raise
temp. of 1 ____ of agsubstance 1 K
For H2O: If s.h. = 1 cal/g-K, then m.h.c. = 18 cal/mol-K.

i.e., m.h.c. = molar mass X s.h.

We calculate the heat a substance loses or gains using:

AN
q = m cP DT D q = /– m cf or v
+

(for within a given (for state-of-matter

state of matter
, i.e., , i.e., when
transitions
when temp changes) when temp is constant)
where
q = heat (usually in J)
m = amount of substance (in g or mol)
cP = heat capacity (cP,S = cP,L = cP,G)
DT = temperature change (K or oC...doesn’t matter)
cf or v = heat of fusion (s/l) or heat of vaporization (l/g)
 Typical Heating Curve

q)
(– G
ed cP,G
ov L/G
em
a tr cv
h e
 L
Temp.

cP,L
S/L ) 
cf d (+q q = m cP DT
S d e
a d
cP,S a t
h e
q = +/– m cf or v

HEAT
 How do magnitudes of > cf
cv and compare?
IMFs must be
completely overcome KE must be increased
for particles to enough to allow particles
enter gaseous phase to slide relative to each
other, but IMFs still in effect
e.g., For H2O... cf = 333 J/g , cv = 2256 J/g
SUMMARY: Intro to Heating Curves

q )
(– G
v ed cP,G
mo L/G
t re
a cv
he
 L
Temp.

cP,L
S/L ) 
q
cf d (+ q = m cP DT
S d e
a d
cP,S a t
h e
q = +/– m cf or v

HEAT
 REVIEW: Heating Curve

q )
(– G
v ed cP,G
mo L/G
t re
a cv
he
 L
Temp.

cP,L
S/L ) 
q
cf d (+ q = m cP DT
S d e
a d
cP,S a t
h e
q = +/– m cf or v

HEAT
 Find the enthalpy change when Phase Change Constants
for Water
82.4 g of ice at –13.5 C turns to
o

water at 72.8oC. cP,ice = 2.077 J/g-K

cf = 333 J/g
warm ice to 0oC:
cP,water = 4.18 J/g-K
q = m cP DT
cv = 2256 J/g
q = 82.4 (2.077) (0 – –13.5) cP,wv = 2.042 J/g-K
q = 2310 J
melt ice at 0oC: 100 C –
o

q = +m cf
q = +82.4 (333) = 27439 J 0 C –
o

heat water from 0oC to 72.8oC:

q = m cP DT
q = 82.4 (4.18) (72.8 – 0) qtot = DH = 54.8 kJ
STOP = 25075 J
 REVIEW: Heating Curve

q )
(– G
v ed cP,G
mo L/G
t re
a cv
he
 L
Temp.

cP,L
S/L ) 
q
cf d (+ q = m cP DT
S d e
a d
cP,S a t
h e
q = +/– m cf or v

HEAT
Using the constants given, find the enthalpy change when 679 g
of water at 27.4oC are converted into water vapor at 121.2oC.
cf = 333 J/g
cv = 40.61 kJ/mol 100oC –
cP,L = 4.18 J/g-K
cP,S = 2.077 J/g-K 0oC –

cP,G = 36.76 J/mol-K

Heat liquid… q = m cP DT
= 679 g (4.18 J/g-K) (100 – 27.4) = 206 kJ
Boil liquid… q = +m cv = +37.72 mol (40.61 kJ/mol) = 1532 kJ
Heat gas… q = m cP DT
= 37.72 mol (36.76 J/mol-K) (121.2–100) = 29.4 kJ

STOP DH = + 1770 kJ
 REVIEW: Heating Curve

q )
(– G
v ed cP,G
mo L/G
t re
a cv
he
 L
Temp.

cP,L
S/L ) 
q
cf d (+ q = m cP DT
S d e
a d
cP,S a t
h e
q = +/– m cf or v

HEAT
With a coffee-cup calorimeter, a reaction is
carried out under constant pressure conditions.
-- Why is the pressure constant?
calorimeter isn’t sealed, and r r. .
su sy s
atmospheric pressure is constant
If we assume that no heat is
exchanged between the system
and the surroundings, then the heat
‘something-in-the-system’ loses
must equal the heat ‘something-
else-in-the-system’ gains.

i.e., qgained = –qlost OR qlost = –qgained

+ =– – – =– +
76.2 g of tungsten at 413oC are added
to 177 g of 22.0oC water. If the specific
heat of tungsten is 0.134 J/g-K, find
the system’s final temp. (As you recall,
water’s specific heat is 4.18 J/g-K.)

q = m cP DT (W) qlost = –qgained (H2O)

q = +/– m cf or v (m cP DT)W = –(m cP DT)H2O

76.2 (0.134) (Tf – 413) = –177 (4.18) (Tf – 22)

10.21 Tf – 4217.06 = –739.86 Tf + 16276.92
750.07 Tf = 20493.98
Tf = 27.3oC STOP
REVIEW: Constant-Pressure Calorimetry
i.e., coffee-cup calorimetry
We assume that no heat is
exchanged between the system and
surroundings, only between system
components. So...
qgained = –qlost OR qlost = –qgained

q = m cP DT Equations for q = +/– m cf or v

finding heat
(for within a given (for state-of-matter
state of matter) exchanged transitions)
25.2 g of ice at –8.0oC are cf = 333 J/g
dropped into 215 g of 93.5 C o
cv = 40.61 kJ/mol
vegetable oil. The oil’s
cP,L = 4.18 J/g-K
specific heat is 1.67 J/g-K;
cP,S = 2.077 J/g-K
the constants for H2O are
shown at right. Find the cP,G = 36.76 J/mol-K
system’s final temp.
(H2O) qgained = –qlost (oil)

heat ice 25.2 (2.077) (0 – –8)

melt ice + 25.2 (333) = –215 (1.67) (Tf – 93.5)
heat water + 25.2 (4.18) (Tf – 0)

418.72 + 8391.6 + 105.34 Tf = –359.05 Tf + 33571.18

q = m cP DT 464.39 Tf = 24760.86
q = +/– m cf or v Tf = 53.3oC STOP
REVIEW: Constant-Pressure Calorimetry
i.e., coffee-cup calorimetry
We assume that no heat is
exchanged between the system and
surroundings, only between system
components. So...
qgained = –qlost OR qlost = –qgained

q = m cP DT Equations for q = +/– m cf or v

finding heat
(for within a given (for state-of-matter
state of matter) exchanged transitions)
 When 50.0 mL of 0.100 M AgNO3 and 50.0 mL of
0.100 M HCl are mixed in a coffee-cup calorimeter,
the mixture’s temperature increases from 22.30oC to
23.11oC. Calculate the enthalpy change for the
reaction, per mole of AgNO3. ** Assume:

AgNO3 + HCl  AgCl + HNO3 -- mixture cP = cP of H2O

-- mixture mass = 100 g
0.05 L, 0.05 L,
0.1 M 0.1 M 338.58 J
0.005 mol 0.005 mol DH =
0.005 mol AgNO3
q = m cP DT kJ
– 67.7
= 100 (4.18) (23.11–22.30) mol AgNO3
= 338.58 J (for 0.005 mol AgNO3) STOP
 Combustion reactions are studied using constant-
volume calorimetry.

This technique
requires a
bomb calorimeter.

heat capacity of
-- The ___________
the bomb calorimeter
(Ccal) must be known.

unit is J/K
(or the equivalent) bomb calorimeter
-- As with constant-pressure calorimetry, we assume
that no energy escapes into the surroundings. So the
magnitudes of heat absorbed by the calorimeter and
the heat given off by the reaction are... equal.
Solve bomb
calorimeter problems
by unit cancellation.
A 0.343-g sample of propane, C3H8, is
burned in a bomb calorimeter with a heat
capacity of 3.75 kJ/oC. The temperature of
the material in the calorimeter increases
from 23.22oC to 27.83oC. Calculate the
molar heat of combustion of propane.
kJ
3.75 o (27.83oC–23.22oC)
C
17.29 kJ  44 g 
 
0.343 g  1 mol C3H8 

– 2220 kJ/mol
STOP
 Chemical
Thermodynamics
Thermodynamics involves
enthalpy changes AND
changes in order/disorder.
spontaneous processes: ones that occur without
outside intervention
“thermodynamically
favorable”

Spont. processes tend to be EXO / ENDO

(i.e., have (–)
___ enthalpy changes) and tend to
result in INCREASED / DECREASED order.
reversible process: “undo exactly what you did and
you’ve got what you started with”
-- both system and surroundings go back
to original states
-- e.g., changes of state
add X J
ice @ 0oC water @ 0oC
take away X J
irreversible process: getting back what you started with
requires more than just an “undo”
-- we can restore the original system, but the
surroundings will have changed (we had to do work)
-- e.g., a gas expanding into an evacuated space

piston

vacuum gas
 Points of note:

1. Whenever a system is in equilibrium, we can go

reversibly between reactants and products.
2. In any spontaneous process, the path between
reactants and products is irreversible.
3. Thermodynamics refers to the direction of a
reaction, not its speed. STOP
 Entropy (S) -- Processes in which the system’s
disorder increases tend to occur
“chaos”
DS = Sspontaneously.
f – Si
“randomness”
+ DS  P are more __________than
disordered R
– DS  P are more __________
ORDERED than R
large (or high) entropy = large # of microstates = very disordered
small (or low) entropy = small # of microstates = less disordered
 Entropy at the Particle Level
There are three types of motion,
each having kinetic energy (KE).
-- translational, vibrational, rotational
-- The more KE we have, the ______more
entropy we have. (i.e., the more microstates are possible)

In general… As T / , S /
and… Ssolid < Sliquid < Sgas

condensin
Process freezing melting boiling
g
Sign of – + – +
DS
Entropy increases when:
1. the number of gas particles increases
2 NH3 N2 + 3 H2 +DS
fewer bonds;
fewer restrictions on motion of atoms;
more degrees of freedom;
more possible microstates
2. liquids or solutions 3. gases are formed
are formed from solids from liquids or solids
 Which has the greater entropy?

1 mol O2(g) @ 300 K or 1 mol O2(g) @ 500 K

(same volume)
1 mol KCl(s) @ 300 K or 1 mol HCl(g) @ 300 K

2 mol HCl(g) @ 300 K or 4 mol HCl(g) @ 300 K

(same volume)
1 mol HCl(g) @ 300 K or 1 mol Ar(g) @ 300 K
(same volume)

2 mol HCl(g) @ 300 K or 2 mol HCl(g) @ 300 K

(in a 10-L vessel) (in a 5-L vessel) STOP
zeroth law of thermodynamics:
If Object A is in thermal equilibrium with
Object B and Object B is in thermal
equilibrium with Object C, then...
Obj. A is in thermal eq. with Obj. C.
first law of thermodynamics:
in essence,
the law of conservation of energy
Energy morphs between its
various forms, but the total
“mass-
amount remains the same.
and-
energy- Often expressed as:
together” (E is
internal DE = q + w
energy)
second law of thermodynamics:
The total entropy of a system
NEVER decreases over time.
In the rare instance that a
system is isolated and is the
site of a reversible process... DSsys = 0.

Otherwise... DSsys > 0

THIS is definitely the case
spontaneous
for all ____________
irreversible processes.
(i.e., __________)

Entropy is NOT conserved; it is constantly increasing.

third law of thermodynamics:
The entropy of a pure,
crystalline substance at
absolute zero is… ZERO.
-- that would be a state
of perfect order
(“Mission Impossible.”)
SUMMARY: The Laws of Thermodynamics
Zeroth: If two objects are each in thermal
equilibrium with a third, then they are in
thermal eq w/each other (i.e., at the same
temp).
First: Energy is conserved, i.e., the change in
any system’s internal energy DE equals the
work done on/by the system plus the heat
flowing into/out of the system: DE = q + w
Second: The total entropy of a system never
decreases over time.
Third: The entropy (i.e, disorder) of a pure
 REVIEW: Entropy
Entropy S is a measure of the disorder (or
chaos, or randomness) of a system.
Because there is NO system that is perfectly
ordered, a system’s absolute entropy can
never be zero or negative. The change in a
system’s entropy, however, CAN be negative
(for systems that become more orderly, e.g.,
a substance freezing) OR positive (for
systems that become more chaotic, e.g., a
substance boiling). Here, we do some
calculations with entropy changes.
For a system in which heat is q
S 
transferred at constant temperature… T
-- temp must be in Kelvins i.e., heat (energy)
-- common unit for entropy  JK temperature

Find the change in entropy when 87.3 g of water

vapor condense, given that water’s heat of
vaporization is 5.99 kJ/mol.
 1 mol  kJ 
– 87.3 g   5.99 
q – m cv  18 g  mol 
S  = 
T T 373.15 K

= –0.0779 kJK = –77.9 JK

 standard molar entropies, So: molar entropy
values
of pure substances in their standard states
elements and 25 C and
o

compounds ~1 atm of pres.

So values typically… actually, at 1 bar = 0.987 atm
-- are NOT zero
-- /increasing molar mass
w

-- /increasing # of atoms in formula

w

For a chemical reaction…

DSo = SnSoP – SmSoR i.e., DS = P – R

(n and m are the coeff. for each substance)
Calculate the PREDICT:
standard P4 -- smallest So?
entropy PCl5 -- largest So?
change for… (–) -- sign of DSo?

P4(s,white) + 10 Cl2(g)  4 PCl5(g)

177 223 353
(need tabulated values of So, in J/mol-K)
DSo = PRODUCTS – REACTANTS
DSo = (4) (353) – [ (1) (177) + (10) (223) ]
mol J mol J mol J
mol-K mol-K mol-K

= –995 J/K STOP

Enthalpy changes (DH) and entropy changes (DS)
both have a “say” in whether or not a process is
spontaneous, i.e., IF it is thermodynamically favorable.
We know that
processes having... ...tend to be...
+DH NOT t.f. (i.e., NOT spont.)
–DH YES! t.f. (i.e., YES! spont.)
+DS YES! t.f. (i.e., YES! spont.)
–DS NOT t.f. (i.e., NOT spont.)
But the “final word” on
t.f./spontaneity is spoken by the
Gibbs free energy equation:
DG (–) = YES!
Josiah Willard Gibbs DG = DH – TDS
1839–1903
DG (+) = NOT
DG (–) means... YES! t.f./spont. as written, L to R
DG (+) means... NOT t.f./spont. as written, L to R
DG = 0 means... AT equilibrium (but YES!
t.f./spont.
R to L...!)
N2(g) + 3 H2(g) 2 NH3(g)

Say we start with only...

...N2 and H2: ...NH3:
We know: YES! t.f./spont.  NOT t.f./spont. 
Thus... DG must be...(–) DG must be...(+)
More often, we calculate DG first. THIS tells us... STOP

whether the process is thermodynamically favorable.

 REVIEW: Change in Gibbs Free Energy
The final arbiter of whether a process is thermo-
dynamically favorable (i.e., spontaneous) in the left-to-
right direction as it is written in the reaction equation is
the change in Gibbs free energy:

DG = DH – TDS
If DG < 0: thermodynamically favorable, L to R.
If DG > 0: NOT thermodynamically favorable, L to R.
If DG = 0: AT equilibrium.
, We see that the change in enthalpy DH and change in
entropy DS both play a role in determining spontaneity.
 standard free energies of formation, DGfo
-- have been tabulated for pure solids, pure liquids,
and gases at ~1 atm pressure, and 1 M solutions
-- For elements in their standard states… DGfo = 0
-- For a reaction, the standard free-energy change
is found by…

DGo = SnGfoP – SmGfoR

i.e., DGo = P–R

DG says WHICH WAY a rxn
will proceed, but it says
NOTHING about the rxn rate.
Calculate the standard
free-energy change for… PCl3(g) + Cl2(g)  PCl5(g)
–286.3 0 –324.6
tabulated DGfo’s (in kJ/mol)

DGo = P – R
= [1(–324.6)] – [1(–286.3)]
mol kJ mol kJ
mol mol STOP

= –38.3 kJ

rxn. is t.f./spont.
as written
(i.e., L to R)
 REVIEW: Change in Gibbs Free Energy
The final arbiter of whether a process is thermo-
dynamically favorable (i.e., spontaneous) in the left-to-
right direction as it is written in the reaction equation is
the change in Gibbs free energy:

DG = DH – TDS
If DG < 0: thermodynamically favorable, L to R.
If DG > 0: NOT thermodynamically favorable, L to R.
If DG = 0: AT equilibrium.
, We see that the change in enthalpy DH and change in
entropy DS both play a role in determining spontaneity.
In general, for SOLIDS
dissolving in liquids, as
temp. increases,
solubility... increases...
and for GASES
dissolving in liquids, as
temp. increases,
solubility... decreases.
The change in Gibbs
free energy equation...
DG = DH – TDS
...can give us
some insight
as to WHY.
When SOLIDS dissolve
in liquids, e.g.,
MN(s)  M+(aq) + N–(aq)
the change in entropy DS
is... (+), i.e., there is MORE
disorder/randomness.
-- more particles on P side
-- more motion on P side

+
DG = DH – TDS
+ So as T increases, DG
becomes more...(–),
i.e., thermodynamically
ALWAYS (–) favorable (spontaneous).
 When GASES dissolve
in liquids, e.g.,
G(g)  G(aq)
the change in entropy DS
is... (–), i.e., there is LESS
disorder/randomness.
-- less motion on P side

+–
DG = DH – TDS
So as T increases, DG
(+),
becomes more...
i.e., NOT thermo-
dynamically favorable
ALWAYS (+)
STOP
(NOT spontaneous).
 REVIEW: Free Energy
The change in Gibbs free energy tells if a process is
thermodynamically favorable (or NOT) in the left-to-
right direction. This change for a process is defined:

DG = DH – TDS
If DG < 0: thermodynamically favorable, L to R.
If DG > 0: NOT thermodynamically favorable, L to R.
If DG = 0: AT equilibrium.
Standard free energies of formation DGfo have the
value of ZERO for elements in their standard states.
For compounds, these values can be looked up.
 Free Energy and Temperature
From DG = DH – TDS, we see
that DG varies with temperature.
-- When T changes, so does DG.
-- DH and DS change little with temperature.

EX. (a) Calculate DHo, DGo, and DSo for…

2 NO(g) + O2(g)  2 NO2(g)

DHfo (kJ/mol) 90.3 0 33.2

DGfo (kJ/mol) 86.7 0 51.8
So (J/mol-K) 210.7 205 240
 2 NO(g) + O2(g)  2 NO2(g)

DHfo (kJ/mol) 90.3 0 33.2

DGfo (kJ/mol) 86.7 0 51.8
So (J/mol-K) 210.7 205 240

DHo = [2(33.2)] – [2(90.3)] DHo = –114.2 kJ

exo/endo?

DGo = [2(51.8)] – [2(86.7)] DGo = –69.8 kJ

spont/non?
NO INFO about rate!

DSo = [2(240.0)] – [205.0 + 2(210.7)] DSo = –146.4 J/K

more/less disorder?
 2 NO(g) + O2(g)  2 NO2(g)

DHfo (kJ/mol) 90.3 0 33.2

DGfo (kJ/mol) 86.7 0 51.8
So (J/mol-K) 210.7 205 240

DHo = –114.2 kJ DGo = –69.8 kJ DSo = –146.4 J/K

(b) Estimate DG at 400 K. (Remember: DH and DS

DG = DH – TDS vary very, VERY little w/T.)

= –114,200 J – [400 K(–146.4 J/K)]

= –55,600 J = –55.6 kJ NO INFO about rate!
STOP
 REVIEW: Free Energy and Temperature
The change in Gibbs free energy is found from the
equation:

DG = DH – TDS
We see that DG varies with temperature. As it turns
out, however, DH and DS at any particular temp. are
LITTLE different from DHo and DSo (i.e., at 25oC). So
as long as we have access to tabulated values in
order to calculate DHo and DSo for a process, we can
get a good estimate of the value of DG (and thus
determine spontaneity) for that process at ANY temp.
Estimate the normal boiling pt. of ethanol, CH3CH2OH.
At the NBP… CH3CH2OH(l) CH3CH2OH(g)
Strategy: Realize that DG = 0.
Find DS and DH
(i.e., DSo and DHo).
Solve for T in DG = DH – TDS.
L G
So (J/mol-K) 160.7 282.7
DHfo (kJ/mol) –277.7 –235.1
~
DS = DS = 122 J/K
o DH ~
= DHo = 42.6 kJ
0 From H 42,600 J
DG = DH – TDS… T  = 349 K (76oC)
S 122 J/K
Taking a closer look, we found...
DH = 42,600 J; DS = 122 J/K
We estimated the NBP of
76 oC;
ethanol to be ___
78 oC.
the actual is ___
“tipping point” 51K
temp.
0
+ 3
+
DG = DH – TDS
At ___
78 oC, DG = 0.
As T increases, DG becomes...(–)
-- spont., L to R
As T decreases, DG becomes...(+)
-- NONspont., L to R (i.e., spont. R to L) STOP
For a reaction, DGo is the standard free-energy change
if all substances in the reaction are at standard
conditions. If we DON’T have standard conditions, the
free-energy change DG
is found using...

DG = DGo + RT ln Q

R = 8.314 J/mol-K
T = absolute temp.
Q = rxn. quotient

Comparatively few reactions

in industry take place under
standard conditions.
non-standard T Calculate DG at 198 K,
two non- given the following:
standard Ps N2(g) + 3 H2(g) 2 NH3(g)
Look up! 1.0 atm 3.0 atm 0.50 atm
DGfo (kJ/mol)
0 0 –17

DGo = 2(–17) = –34 kJ DG = DGo + RT ln Q

(0.50)2
Q 3 = 0.00926
(1.0)(3.0)
DG = –34,000 + 8.314 (198) (ln 0.00926) STOP

DG = –41.7 kJ (thermodynamically favorable/spont.)

REVIEW: Free-Energy Changes under
Non-standard Conditions
Recall that standard conditions are:
-- temperature of 25oC (i.e., 298 K)
-- gas partial pressures of ~1 atm
-- solution concentrations of 1 M

Under any other conditions, we find the

change in the Gibbs free energy using:

DG = DGo + RT ln Q
Imagine a system that is
at equilibrium, at some
temperature T. By
definition, when a system
is AT equilibrium...
DG = 0 AND Q = K.
0 K
DG = DGo + RT ln Q

DGo = –RT ln K For a given process, DGo is FIXED,

so K changes as T changes.
–DGo
RT For gaseous rxns, the K is Kp;
K=e
DGo = –RT ln K Calculate K and DG at 135oC for…
–DGo
H2(g) + Cl2(g) 2 HCl(g)
RT 2.5 atm 2.5 atm 0.5 atm
K=e
DGfo (kJ/mol)
0 0 –95

(spont. under
DG = 2(–95) = –190 kJ
o
std cond.)
–(–190,000)
(8.314)(408)
K408 K = e = 2 x 1024

DG = DGo + RT ln Q
(0.5)2
= –190,000 + 8.314(408)(ln )
(2.5)(2.5)
= –2.0 x 105 kJ STOP
Thermodynamic quantities have been measured and
tabulated – not only for substances – but also for
many simple ‘building-block’ reactions. Hess’s law
allows us to manipulate several ‘building-block’ rxns
such that we can find thermodynamic values for a
more-complicated reaction. We do this by taking
multiples of the building-block rxns and manipulating
their forward-backward nature... and adding them.

Using
Hess’s law is
somewhat like finding
the area of a composite
shape by adding or
subtracting the areas of
simpler shapes. Germain Henri Hess (1802 – 1850)
 Calculate the heat of reaction for the combustion of
sulfur to form sulfur dioxide.
2 SO2(g) + O2(g) 2 SO3(g)(DH = –198.2 kJ)

S8(s) + 12 O2(g) 8 SO3(g)(DH = –3161.6 kJ)

S8(s) + 8 O2(g) 8 SO2(g) (TARGET)

S8(s) + 12 O2(g) 8 SO3(g) (DH = –3161.6 kJ)

82 SO
SO33(g)
(g) 82SO
SO2(g)
2(g) +
+ 4OO 2(g) (DH
2(g) (DH==+198.2
+792.8kJ)
kJ)

S8(s) + 8 O2(g) 8 SO2(g) DH = –2368.8 kJ

Calculate DH for the reaction… 5 C + 6 H2C5H12

C5H12 + 8 O2 5 CO2 + 6 H2O (DH = –3535.6 kJ)

C + O2 CO2 (DH = –393.5 kJ)
H2 + ½ O2 H2O (DH = –285.8 kJ)

5 CO2 + 6 H2O C5H12 + 8 O2 (DH = +3535.6 kJ)

5 C + 5 O2 5 CO2 (DH = –1967.5 kJ)

6 H2 + 3 O2 6 H2O (DH = –1714.8 kJ)

5 C + 6 H2 C5H12 DH = –146.7 kJ
Had the question been,
“Calc. DH per mole of C…” answer is: –29.3 kJ/mol C STOP