CHM 135: Last Third

Course text: "Chemistry: the Molecular Nature of Matter and Change

9e, by Silberberg and Amateis
Ch. 6: Thermochemistry:
Energy Flow and Chemical Change
Ch. 20: Thermodynamics:
Entropy, Free Energy, and Reaction Direction
Ch. 21: Electrochemistry:
Chemical Change and Electrical Work

It’s all about ENERGY NASA, 2000

 CHM 135: Last Third

It’s all about energy.

 CHM135, part 3
Thermodynamics: Energy, Energy Conversion & Flow
Thermodynamics = study of
energy and its conversion from
one form to another
• Thermodynamics is useful because it
has so many practical applications,
including predicting the direction of
chemical reactions.
• Among other things, this knowledge
helps us learn how to capture and
store energy efficiently and safely.
Thermochemistry (CH 6) = a branch
of thermodynamics, which highlights
how heat is involved in chemical and
physical transformations 3
 CHM135, part 3
Internal Energy
There are two basic kinds of energy:
potential energy (Ep) and kinetic energy (Ek).
EP is stored energy EK is the energy of motion = 1/2 mv2
Potential Energy Potential Energy
+
Kinetic Energy Kinetic Energy

➢ The internal energy, E, of a system is the sum of all energy

(potential and kinetic) of everything in that system.

4
 CHM135, part 3
Chemical Energy and Energy Flow
There are two basic kinds of energy:
potential energy (Ep) and kinetic energy (Ek).
EP is stored energy EK is the energy of motion = 1/2 mv2
Potential Energy Potential Energy
+
Kinetic Energy Kinetic Energy

On the molecular scale, we think in terms of:

• chemical bond energy = potential energy stored in molecular bonds
EXAMPLE: Many of our cellular processes are
driven by energy released upon hydrolysing a
phosphate bond in an adenosine triphosphate
Figure from Essentials (ATP) molecule to create more stable
of Cell Biology, 2010, products: ADP and inorganic phosphate.5
Nature Education
 CHM135, part 3
Chemical Energy and Energy Flow
There are two basic kinds of energy:
potential energy (Ep) and kinetic energy (Ek).
EP is stored energy EK is the energy of motion = 1/2 mv2
Potential Energy Potential Energy
+
Kinetic Energy Kinetic Energy

On the molecular scale, we think in terms of:

• chemical bond energy = potential energy stored in molecular bonds
• energy of molecular motion (translational, rotational and vibrational)
• sometimes also called “thermal energy”
• temperature is a common measure of the energy of mol. motion
6
 CHM135, part 3
Temperature Reflects Molecular Energy of Motion
Water at 298 K (room temp.) Water ice at 5 K

By Danski14 - Own work, CC BY-SA 3.0,

Molecular simulation by Prof. Chris Rawley
https://commons.wikimedia.org/w/index.
7
(Memorial U. Newfoundland) php?curid=19178246
 CHM135, part 3
Energy, Change in Energy and Energy Flow
Energy: the capacity to do work or supply heat.
Change in Energy = work + heat
of a system done on flow in to
the system the system
DE = w + q

• Energyis measured in Joules or kiloJoules These cyclists are using

up (losing) energy both
1 Joule = 1 kgm2/s2 because they are doing
1 calorie = 4.184 J (small) work and because they
are producing heat.
1 dietary “Calorie” = 1000 calories = kcal
8
 CHM135, part 3
Critical Concept: Conservation of Energy (E)
Energy cannot be created or destroyed (although as we will discuss,
energy can be converted from one form to another).
∆𝑬𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = 0 1st law of thermodynamics

We are familiar with this idea on the macroscopic scale:

Potential Energy Potential Energy
+
Kinetic Energy Kinetic Energy

• Note that is the total energy of the universe that is conserved.

• Does all the PE become KE of the ball in the real world?
• What good is knowing about universal energy conservation to us?
We are probably only interested in tiny corner of the universe…
9
 CHM135, part 3
Universe is Divided into the System and the Surroundings
The system is chosen to include whatever you are focusing on
(and things that cannot usefully be separated from that).
The surroundings is everything not in the system.
System + Surroundings = Universe
If energy leaves the system, it must enter the surroundings (and visa
versa). Thus, we can determine the energy change of a system of
interest by measuring the energy change in the surroundings.

surroundings
system
10
 CHM135, part 3
Energy Exchange between the System and Surroundings
Any change in the energy of the system must be accompanied by
an equal magnitude change in the energy of the surroundings,
but the signs of these changes must be opposite.
e.g., if a reaction occurs in a beaker of water and the temperature of
the water increases, we can deduce that the reaction produced heat.
Moreover, if we can measure how much heat flowed into the water,
we know how much heat the reaction produced.

Restatement of the 1st law of thermodynamics:

∆𝐸𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 +∆𝐸𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0

11
 CHM135, part 3
Universe is Divided into the System and the Surroundings
∆𝐸𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 +∆𝐸𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0
For practical reasons, we often use a barrier to limit the surroundings
in thermochemical experiments. Its role is to stop (or at least
minimize) transfer of energy (heat and work).

Thus, we can determine the energy change in system of interest

by measuring energy change in limited, well-defined surroundings.

limited
surroundings Barrier to
energy flow
system
12
 CHM135, part 3
Sign Conventions in Thermodynamics
The picture can change depending on your point of view.

unidentified artist

In thermodynamics, the sign of each quantity reflects the

system’s perspective
 CHM135, part 3
Sign Conventions in Thermodynamics
In thermodynamics, all signs reflect the system’s perspective

Let’s choose system = cyclist in red jersey

The system is losing energy, so DEsystem is negative Energy Out
(DE <0)
(from the cyclists’ perspective).
What are the signs of w and q?

DE = w + q
These cyclists are using
up (losing) energy both
How could energy of the system (= cyclist) be because they are doing
work and because they
increased? are producing heat.
 CHM135, part 3
Signs are Defined from the System’s Point of View
We will find it useful to think about the energy and energy flow
in chemical rxns by making diagrams.
For example, say you do a reaction that releases energy (produces heat or
does work). The system loses energy.
Energy is released in the reaction because the reactants are higher in
energy than the products. surroundings
Ereactants
Energy

∆𝑬 < 𝟎
decreases
energy

∆𝑬 = 𝑬𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑬𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 < 𝟎

system ∆𝑬 > 𝟎
Eproducts

(Note that “system” or “reaction” is implied here, and could be

included as a subscript, but often is not explicitly written out) 15
 CHM135, part 3
Internal Energy (E) is an example of a State Function
• State function: A function or property whose value depends
only on the present state (condition) of the system.
Stated another way… the path does not matter
 CHM135, part 3
State Functions: Path Independence
EXAMPLE: flying between Toronto and Montreal:
(1) Toronto – Montreal, (2) Toronto – Saskatoon – Montreal

• Position is a state function (dest. Montreal, regardless of path)

• Jet fuel and ticket prices are not state functions 17
 CHM135, part 3
More about State Functions and Path Independence
• We have met (and used) several state functions already: E, V, P
• The change (D) in the value of state functions can be calculated
by simply subtracting the initial from the final state:
∆𝑉 = 𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
∆𝐸 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
…
• Note that if the final and initial states of a state function are the
same, then the change of that state function is zero.
• In Chemistry and Physics, state functions are represented with
CAPITAL LETTERS.
• State function can be usefully Einitial

Energy
∆𝑬 = 𝑬𝒇𝒊𝒏𝒂𝒍 - 𝑬𝒊𝒏𝒊𝒕.
represented on a scale: Efinal 18
 CHM135, part 3
State function?
Consider possible ways to burn octane:
in a barrel or in the engine of a car

(mostly)

• Two different paths for the energy change of a system.

• Even though q and w for the two paths are different,
the total DE is the same for both.
• q and w are not state functions. 19
 CHM135, part 3
Transfer of Energy as Heat, Work or Both
• Most changes to the internal energy of a system
involve transfer of both heat and work.
Einitial
Energy

DE = w + q
Ice cube
Efinal

• However, first let’s consider examples in which

energy transfer is only as heat and only as work

20
 CHM135, part 3
Transfer of Energy: as HEAT (q) Only
• Energy: the capacity to do work or supply heat.
0
DEsys = w + q
Example of energy transferred as heat (q) only (w ≈ 0).
Ice cube

• The system (initially hot coffee) releases heat.

heat (q) (also called “thermal energy”) will flow from
higher-temperature objects to lower-temperature objects.
Eventually, the objects will reach the same temperature.
21
 0 CHM135, part 3
Transfer of Energy: as HEAT (q) OnlyDE (sys) = w +q
0
DE = w + q
Representing this on an energy scale:
Energy (of the system)

Einitial

Energy
Heat (q) released to
the surroundings
Efinal Efinal
DE < 0 q<0 Heat (q) is absorbed
from the surrounding

Einitial
DE > 0 q>0
22
 CHM135, part 3
Transfer of Energy: as WORK (w)
• Energy: the capacity to do work or supply heat.
DE = w + q
Work (w): Mechanical work is the product of force (F) and
distance (d).
w=F×d
The larger the required force, or the longer the distance an
object is moved, the more work is done on it.

(Electrical work is another kind of work. We will discuss

electrical work near the end of the semester.) 23
 CHM135, part 3
Transfer of Energy: as WORK (w) Only (q=0)
0
DEsys = w + q
Gas forming reaction in an insulated container that is attached to
a piston-cylinder assembly that pushes against something.
PUSH

Zn(s) + 2H+(aq) + 2Cl-(aq)

Energy

H2(g) + Zn2+(aq) + 2Cl-(aq)

Einitial
The system pushes the piston out,
doing work on the surroundings.
The system releases (loses) energy.
Efinal
DE = w < 0 24
 CHM135, part 3
Expansion Work
• The scenario on the previous slide is an example of expansion work,
the work done when the volume of a system changes in the
presence of an external pressure.

system does work

(loses energy)

• Expansion work is also often known as pressure volume (PV) work,

because the amount of work done depends on both P and V
• At constant pressure (P = Psurr),
𝑤 = −𝑃∆𝑉 = −𝑃 𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
➢ More work is done when the volume change (DV) is larger
and/or when pushing against a higher external pressure.
25
 CHM135, part 3
Expansion Work: units

system does work

(loses energy)

• You will have many opportunities to calculate PV work in the

homework, problem solving sessions and tutorials.
• For this, it will be useful to realize that the units of work, heat
and energy must be the same. In SI, they are in Joules (or in kJ).
• Here is a handy conversion between Joules and our most
commonly used units of pressure and volume:
101.3 𝐽 = 1 atm.× 𝐿
26
 CHM135, part 3
Expansion Work: Why is there a Negative Sign?
• Expansion work: at constant pressure,
𝑤 = −𝑃∆𝑉 = −𝑃(𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 )
The negative sign is required to fit with the convention that signs
reflect the system’s perspective.
Consider a system that expands against a pressure :
∆𝑉 > 0

• P, which is the constant pressure of the surroundings, is always > 0.

• The system does work. It loses internal energy by doing this work.
• Following our sign convention, it must be that w < 0, DE < 0
We calculate: 𝑤 = −𝑃∆𝑉 < 0  27
 CHM135, part 3
Expansion Work: Example
The explosion of 2.00 mol of solid TNT with an initial volume of
approximately 0.274 L produces gasses with a volume of 448 L at
room temperature and pressure. How much expansion work is
done during the explosion? Assume P = 1 atm

28
 CHM135, part 3
T Thermochemistry
Some of the highlights so far from CH6

• Internal Energy (E) is transferred as heat and work (w).

∆𝑬 = 𝒘 + 𝒒
• 1st law of thermodynamics: energy of the universe is conserved.
∆𝑬𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = ∆𝑬𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑬𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = 0
• One type of work is pressure volume (or expansion) work.
𝑤 = −𝑃∆𝑉
A system can do work Einitial
(thus losing energy)

Energy
as it expands PUSH
(and visa versa):
Efinal
29
 CHM135, part 3
Multiple Choice Question
In a reaction, if the volume occupied by reactants is larger than the
volume occupied by the products, which must be true?

A) Heat is released into the surroundings

B) Work is done on the system
C) Heat flows into the system
D) (Net) Energy flows into the surroundings
E) All of the above
30
 CHM135, part 3
Multiple Choice Question
In a reaction, if the volume occupied by reactants is larger than the
volume occupied by the products, which must be true?
Which may be true?
A) Heat is released into the surroundings
B) Work is done on the system
C) Heat flows into the system
D) (Net) Energy flows into the surroundings
E) All of the above
31
 CHM135, part 3
Today: Enthalpy – a Practical Accounting System for Energy
It’s all about heat…

32
 CHM135, part 3
Enthalpy: Changes at Constant Pressure
A lot of chemistry is done at nearly constant atmospheric pressure.
Many of my favorite chemical transformations are done in the kitchen.

Enthalpy is a useful scale for keeping track of the energetics of these

constant-pressure transformations, in the kitchen or on the benchtop. 33
 CHM135, part 3
Enthalpy: An Alternative Accounting System for Energy
• Enthalpy (H) is defined as
𝐻 ≡ 𝐸 + 𝑃𝑉
Enthalpy is essentially another accounting system for keeping track of energy.
• This enthalpy “accounting system” is similar to internal energy (E), but does
not include pressure-volume (expansion) work.
• It is useful because Change in Enthalpy (DH)
∆𝑯 = ∆𝑬 + 𝑷∆𝑽
is equal to the amount of heat absorbed or released in a transformation
(a real or imagined reaction) at constant pressure (see next slide). This means
enthalpy change (DH) is often straightforward to determine via experiment.
• We will talk about methods to measure heat transfer, called “calorimetry”
later today or next class. 34
 CHM135, part 3
Change in Enthalpy: Heat Exchange at Constant P
• Change in Enthalpy (DH)
∆𝑯 = ∆𝑬 + 𝑷∆𝑽
is equal to the amount of heat absorbed or released in a transformation
(a real or imagined reaction) at constant pressure.
To see this, start with the expression for change in internal energy we
saw last class:
∆𝑬 = 𝒒 + 𝒘
At constant pressure, and assuming that all work is expansion (PV) work,
we can write: where “qp” denotes heat
∆𝑬 = 𝒒𝒑 + −𝑷∆𝑽 exchange at constant pressure
Rearranging to solve for the heat exchange, we find
Heat flow into a system increases
𝒒𝒑 = ∆𝐸 + 𝑷∆𝑽 = ∆𝑯 the enthalpy of the system. 35
 CHM135, part 3
Terminology: Exothermic and Endothermic Processes
The sign of DH shows whether heat is produced or consumed
in a reaction. This follows or normal sign convention.
DH < 0 Exothermic
Evolved heat flows out
of the system into the
surroundings. Heat is a
product of the reaction.

DH > 0 Endothermic
Heat flows into the system
from the surroundings. Heat
is a reactant.
36
 CHM135, part 3
Enthalpy is a State Function 𝑯 ≡ 𝑬 + 𝑷𝑽

• Like internal energy, enthalpy is a state function, so its change is

straightforward to calculate from the initial and final states:
∆𝐻 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
= 𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙
• It is often useful to represent enthalpies on a scale (just as we do with
internal energy):
B
enthalpy

A → B is an endothermic reaction, thus DHA→B > 0

A
A → C is an exothermic reaction, thus DHA→C < 0
C
37
 CHM135, part 3
The Enthalpy of Water in Different Forms
Consider three forms of H2O: H2O (s), H2O(l) or H2O(g). Each form
has a different enthalpy.
• Which has the largest enthalpy (per mole of H2O)?
• Which has the smallest enthalpy?

form 1 (?)
enthalpy

form 2 (?)

form 3 (?)
38
 CHM135, part 3
Enthalpy Accounting 𝑯 ≡ 𝑬 + 𝑷𝑽

• Enthalpy (DH) and internal energy change (DE) differ in whether they
account for the expansion (PV) work done on the surroundings or done by
the surroundings on the system.

∆𝐻 = ∆𝐸 + 𝑃∆𝑉

• Most reactions involve little (if any) PV work. This is especially true for
reactions involving only solids and liquids, or reactions in which the
amount of gas does not change.
Thus, often (but not always) ∆𝐻 ≈ ∆𝐸
• However, in some cases PV work is substantial. (When?)
In these cases, DH and DE cannot be roughly equated.
39
 CHM135, part 3
Energy Change, Work and Heat: Example
• The compression reaction shown below has DE = –186 kJ.
What is the enthalpy change of this rxn?

50 L 40 L

40
 CHM135, part 3
Enthalpy vs. Internal Energy
The difference is
pressure volume work.
While PV work is usually quite
small, there are exceptions.

For example, the creation of a

large number of gas molecules
(say, via combustion of liquid
fuel thus forming gaseous water
and carbon dioxide) is an
example of large pressure
volume work terms. 41
 CHM135, part 3
Enthalpy Calculations
Given DH for a particular reaction, it is straightforward to compute DH
for related reactions.
For example, let’s say we know the enthalpy of reaction for burning
1 mole of propane: This specifies DH for
the reaction as written
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) DH = –2219 kJ

What is the enthalpy of reaction if we burn 3 moles of propane?

42
 CHM135, part 3
Enthalpy: an Extensive Property
Given DH for a particular reaction, it is straightforward to compute DH
for related reactions.
For example, let’s say we know the enthalpy of reaction for burning 1
mole of propane: This specifies DH for
the reaction as written
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) DH = –2219 kJ
(1) Multiplying a reaction increases DH by the same factor.
3 C3H8(g) + 15 O2(g) → 9 CO2(g) + 12 H2O(l) DH = –6657 kJ
Thus, we see that enthalpy depends on the amount of material present.
This means that enthalpy is an extensive property. Other examples of
extensive properties (properties that scale with the amount of material
present) are volume and mass.
{In contrast, some properties are intensive. Their value does not depend
43
on amount (e.g., temperature, melting point)}
 CHM135, part 3
Thermochemical Equations
Given DH for a particular reaction, it is straightforward to compute DH for
related reactions.
For example, let’s say we know the enthalpy of reaction for burning 1
mole of propane: This specifies DH for
the reaction as written
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) DH = –2219 kJ

Note that the thermochemical equation (balanced rxn with enthalpy

change) above specifies DH for the reaction as written. So, while we often
only specify an energy value (usually in kJ), this is equivalent to:
−2219 𝑘𝐽 −2219 𝑘𝐽 −2219 𝑘𝐽
𝑜𝑟 or 𝑜𝑟
𝑚𝑜𝑙 𝑟𝑥𝑛 𝑎𝑠 𝑤𝑟𝑖𝑡𝑡𝑒𝑛 𝑚𝑜𝑙 𝐶3 𝐻8 (𝑔) 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 5 𝑚𝑜𝑙 𝑂2 𝑔 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
−2219 𝑘𝐽 −2219 𝑘𝐽
𝑜𝑟
3 𝑚𝑜𝑙 𝐶𝑂2 𝑔 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 4 𝑚𝑜𝑙 𝐻2 𝑂 𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
44
 CHM135, part 3
Enthalpy Calculations
Given DH for a particular reaction, it is straightforward to compute DH for
related reactions.
For example, let’s say we know the enthalpy of reaction for burning 1 mole
of propane: This specifies DH for
the reaction as written
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) DH = –2219 kJ
(1) Multiplying a reaction increases DH by the same factor.
3 C3H8(g) + 15 O2(g) → 9 CO2(g) + 12 H2O(l) DH = –6657 kJ
(2) Reversing a reaction changes the sign of DH for a reaction.
3 CO2(g) + 4 H2O(l) → C3H8(g) + 5 O2(g) DH = +2219 kJ
(3) However, note that the physical state is important (especially for
gasses):
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) DH = –2043 kJ 45
 CHM135, part 3
Question
What is DH for the reaction
NO2(g) → 1/2N2(g) + O2(g)
if N2(g) + 2O2(g) → 2NO2(g) has DH = +66 kJ?

A) -33 kJ

B) +66 kJ

C) -66 kJ

D) +132 kJ

46
 CHM135, part 3
Enthalpy: example
Aluminum metal reacts with chlorine with a spectacular display of sparks:
2 Al(s) + 3 Cl2(g) 2 AlCl3(s) ΔH°rxn = –1408.4 kJ

Source: https://www.youtube.com/watch?v=aK85PZX2xNE

47
 CHM135, part 3
Enthalpy: example
Aluminum metal reacts with chlorine with a spectacular display of sparks:
2 Al(s) + 3 Cl2(g) 2 AlCl3(s) ΔH°rxn = –1408.4 kJ

How much heat in kilojoules is released on reaction of 5.00 g of Al?

.
PLAN: (Simplified plan: KEEP TRACK OF UNITS and stoichiometry!)

48
 CHM135, part 3
Heat Capacity
• Heat capacity is the amount of heat (q, or DH) required to raise
the temperature of an object or substance by 1 °C (or 1 K).
𝒒
𝑯𝒆𝒂𝒕 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒚 =
∆𝑻
Things with a high heat capacity require a lot of heat to
increase in temperature. Conversely, these also give off a lot of
heat when they cool down. In essence, high heat capacity
materials act as a good sponge for (or, store of) thermal energy.
In contrast, materials with low heat capacity heat up easily (and
cool down easily), absorbing (and giving off) little heat as they
do so.
49
 CHM135, part 3
Heat Capacity
HOT! HOT! HOT! HOT! HOT! HOT! HOT! HOT! Sand heats up
quickly in strong
sunshine and
cools down
quickly at night
because sand has
low heat
capacity.

Smithsonian Channel: Dance of the shovel-snouted Lizard 50

 CHM135, part 3
Heat Capacity: Types
• Heat capacity is the amount of heat (q, or DH) required to raise
the temperature of an object or substance by 1 °C (or 1 K).
𝒒 𝐽
[𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 ]
𝑯𝒆𝒂𝒕 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒚 = 𝐾
∆𝑻
• Specific Heat Capacity (c): heat capacity per mass (1.00 g)
𝑞 𝐽
𝑐= [𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 ]
𝒎𝒂𝒔𝒔 × ∆𝑇 𝑔∙𝐾
• Molar Specific Heat Capacity (C): heat capacity per mole
𝑞 𝐽
𝐶= [𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 ]
𝒂𝒎𝒐𝒖𝒏𝒕(𝑚𝑜𝑙) × ∆𝑇 𝑚𝑜𝑙 ∙ 𝐾

Our text follows the convention of using a lower-case c for specific heat
capacity and upper-case C for molar heat capacity. However, it is always
safest to look at the units to distinguish between these. 51
 CHM135, part 3
Heat Capacity: Where Does the Energy Go?
• Heat capacity is the amount of heat (q, or DH) required to raise
the temperature of an object or substance by 1 °C (or 1 K).
𝒒
𝑯𝒆𝒂𝒕 𝑪𝒂𝒑𝒂𝒄𝒊𝒕𝒚 =
∆𝑻 Thermally-agitated
peptide molecule.

• The energy (from heat, q) excites both

translational motion of molecules and
vibrations and rotations within and
between molecules.
en:User:Greg L / CC BY-SA

52
 CHM135, part 3
Some Specific and Molar Heat Capacities at 25 °C

NOTE: heat capacity

actually has a small
dependence on
temperature. This
variation is so small
that it can generally be
neglected (unless the
temperature change is
very large, or there is a
phase change).
4.184 extremely high
heat capacity
Sand 0.290 extremely low heat capacity

a At -11 °C 53
 CHM135, part 3
Example
PROBLEM: A layer of copper welded to the bottom of a skillet weighs 125 g.
How much heat is needed to raise the temperature of the
copper layer from 25°C to 300.°C? The specific heat capacity (c)
of Cu is 0.385 J/g∙K.
PLAN: (Simplified
We knowplan:the
KEEPmass (125
TRACK g) and c (0.385 J/g∙K) of Cu and can
OF UNITS!)
find DT in °C, which equals DT in K. We can use the
definition of heat capacity to calculate the heat.

54
 CHM135, part 3
Question
You have two identically prepared Styrofoam cups, each filled with the same
volume of 20 ˚C water and a thermometer. (This arrangement is known as a
“coffee cup calorimeter”.) Into cup #1, you drop 3.00 g of aluminum (c = 0.90
J/g∙K) that is heated to 80 ˚C. Into cup #2, you drop 3.00 g of iron (c = 0.45 J/g∙K)
that is heated to 80 ˚C. Which block (aluminum or iron) gives off more heat as it
cools to the temperature of the water?
A) Aluminum
#1: Aluminum #2: Iron
B) Iron (3 g) (3 g)
C) they give off equal
amounts of heat
D) It is essential to know how
much water is in the cup to solve
this problem.
55
 CHM135, part 3
Question
You have two identically prepared Styrofoam cups, each filled with the same
volume of 20 ˚C water and a thermometer. Into cup #1, you drop 3.00 g of
aluminum (c = 0.90 J/g∙K) that is heated to 80 ˚C. Into cup #2, you drop 3.00 g of
iron (c = 0.45 J/g∙K) that is heated to 80 ˚C.
The temperature of the water in cup #1 increases from 20.0 ˚C to a final
temperature of 28.2 ˚C as the aluminum cools.
What is the final temperature of the water in cup #2 ?
#1: Aluminum #2: Iron
A) 24.1 ˚C (3 g) (3 g)
B) 28.2 ˚C
C) 36.4 ˚C
D) 56.4 ˚C
E) It is essential to know how much water is in the cup
to solve this problem. 56
 CHM135, part 3
Calorimetry
Measuring the Heat of a Chemical or Physical Change

57
 CHM135, part 3
Calorimetry
• Calorimetry is the science of measuring the heat exchanged in
chemical reactions.
In calorimetry, the heat of reaction (qrxn) is measured indirectly
by means of a calorimeter. If the reaction produces heat, the
temperature of the surroundings increases and visa versa.
calorimeter
(surroundings)
q q
reaction qrxn = -qcalorimeter
(system)
q q (desired) (measured)
58
 CHM135, part 3
Constant-Pressure(Coffee-cup
or “Coffee Cup” Calorimetry
calorimeter)

𝑞𝑠𝑦𝑠𝑡𝑒𝑚 (𝑠𝑎𝑚𝑝𝑙𝑒) = −𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 (𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 𝐻2𝑂) lid must be loose

enough to ensure
• Reaction or physical transformation is done in an pressure equalizes
insulated container at constant pressure in a bath with room
(usually water) of known heat capacity.
• Heat generated thus tells us about the enthalpy of rxn
q = qp = DE + PDV = DH
• The heat capacity of the calorimeter (often about
equal to that of the surrounding water) provides the q
link between change in temperature and heat gained
or lost, from which you can determine the enthalpy
change of the system.
𝑞𝑐𝑎𝑙.
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦𝑐𝑎𝑙. = 59
∆𝑇𝑐𝑎𝑙.
 CHM135, part 3
Constant-Pressure(Coffee-cup
Calorimetry:
calorimeter)
qp= -qcal
Example You heat up 22.05 g of a solid to 100.00 °C
and add it to a “coffee cup” calorimeter which
contains 50.00 g water. The water temperature
changes from 25.10 °C to 28.49 °C.
Find the specific heat capacity of the solid.
Assume that the heat capacity of the calorimeter is
just that of the water (cwater = 4.184 J/g·°C – ie, the
coffee cup itself does not absorb heat) and that the
calorimeter itself exchanges a negligible amount of
heat with the universe.
The Plan:

60
 CHM135, part 3
Constant-PressureCoffee-cup
Calorimeter:
calorimeter.
qp = -qcal
Need to determine the specific heat capacity, c, of the solid.
What we know:
system
surroundings
Heat capacities link heat flow with 𝑞
mass and temperature change for 𝑐=
𝑚𝑎𝑠𝑠 × ∆𝑇
both the water and the sample:

61
 CHM135, part 3
𝐽
What might this substance be that has 𝑐 = 0.450 ?
𝑔∙℃

4.184

62
 CHM135, part 3
Calorimetry: 2 Major Types qrxn = -qcalorimeter
1) Constant Pressure or “Coffee Cup” Calorimetry:
measures the heat change at constant pressure such
that (loose lid)
q = qp = DE + PDV = DH
q

2) Constant Volume or “Bomb” Calorimetry:

measures the heat change at constant volume
such that q
0
q = qv = DE + PDV (vessel must be rigid
= DE enough to maintain
constant volume)
63
 CHM135, part 3
Constant-Volume (Bomb) Calorimetry: qv=-qcal
Bomb calorimeters are commonly used to
measure heat of combustion reactions.
sample + O2 (g) → CO2(g) + H2O (g)
Pre-weighted, combustible sample is
placed inside the bomb, which is filled with
oxygen gas and immersed in a water bath.
From measuring the temperature change,
if the heat capacity of the entire
calorimeter is known, the heat flow into
the calorimeter and thus the heat of the insulating layers
reaction can be determined.
qrxn = -qcalorimeter 64
 CHM135, part 3
Constant-Volume (Bomb) Calorimetry: qv=-qcal
Example
When 0.500 g of ethanol, C2H6O, is burned in a bomb
calorimeter, the temperature of both the water and
the calorimeter rise by 9.15oC. Assuming that the bath
contains 250.0 g of water and that the heat capacity
for the calorimeter is 575 J/oC, calculate how much
heat is created in this reaction.

65
 CHM135, part 3
Summary – today we’ve focused on enthalpy
• Enthalpy (H) is a useful, measurable chemical quantity.
DH < 0 → exothermic
𝐻 ≡ 𝐸 + 𝑃𝑉 ∆𝐻 = ∆𝐸 + 𝑃∆𝑉 = 𝑞𝑝
DH > 0 → endothermic
• Enthalpy is a state function, so DH depends only on the difference
between the final and initial values of H. (Path does not matter)
• Enthalpy is an extensive property.
• The heat capacity (c, C) specifies how much heat is required to raise
a substance by 1 °C (or 1 K).
• Calorimetry can be used to determine DHrxn and c.
qrxn = -qcalorimeter
66
Today: Several Ways to Find DH of Any Reaction
CHM135, part 3

Enthalpy

NET
67
 CHM135, part 3
Hess’s Law: Enthalpy Sums
Enthalpy is a state property, thus we know that
The enthalpy change for a process is equal to the sum of the changes
for individual steps (1, 2, …n) of the process.
DHoverall = DH1 + DH2 + ………. + DHn

For example, if you are doing a two-step reaction and each step generates heat,
the enthalpy change of the overall reaction will be the sum of that heat
generated by each of the two steps.
Reactants
(step 1)
Enthalpy

DH1 (overall)
DHoverall = DH1 + DH2
Intermediates
(step 2)
DH2
Products
68
 CHM135, part 3
Hess’s Law: Example DHoverall = DH1 + DH2 + ………. + DHn

• The industrial degreasing solvent methylene chloride

(CH2Cl2) is prepared from by reacting methane with chlorine:
CH4 (g) + 2 Cl2 (g) → CH2Cl2 (g) + 2 HCl (g)
• Calculate DH (in kJ) for this rxn using the following data:
CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g) DH = –98.3 kJ
CH3Cl(g) + Cl2(g) → CH2Cl2(g) + HCl(g) DH = –104 kJ

CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g) DH = –98.3 kJ

CH3Cl(g) + Cl2(g) → CH2Cl2(g) + HCl(g) DH = –104 kJ

CH4(g) + 2Cl2(g) → CH2Cl2(g) + 2HCl(g) DH = –202 kJ

69
 CHM135, part 3
Hess’s Law: Practice DHoverall = DH1 + DH2 + ………. + DHn

The synthesis of ammonia from hydrogen and nitrogen gases is quite

exothermic. The balanced thermochemical equation is:
3 H2 (g) + N2 (g) → 2 NH3 (g) DH = –92.2 kJ
In practice, this reaction is accomplished via a two-step path:
1) 3 H2 (g) + N2 (g) → H2 (g) + N2H4 (g) DH = +95.4 kJ
2) H2 (g) + N2H4 (g) → 2 NH3 (g) DH = ?
What is DH of the second step?
Enthalpy

Reactants 3 H2+ N2
(Overall)
DH = -92.2 kJ
Product 2 NH3 70
 CHM135, part 3
Hess’s Law Summary
Hess’s Law tells us that we can and that enthalpies of
treat reaction statements like reaction can be treated
equations: the same way.
A+B→C+D DH1
+ C+E→F+A DH2
B+E→F+D Net DH = DH1 + DH2

Note that the “steps” do not actually have to be real – they could be
hypothetical or imagined – but they do need to add up to the balanced
reaction equation.
71
Using Hess’s Law to Calculate an Unknown DH
CHM135, part 3

PROBLEM: Two gaseous pollutants that form in auto exhausts are CO

and NO. An environmental chemist is studying ways to
convert them to less harmful gases through the following
reaction:
CO(g) + NO(g) → CO2(g) + ½N2(g) DH = ?
Given the following information, calculate the unknown DH:
Equation A: CO(g) + ½ O2(g) → CO2(g) DHA = -283.0 kJ
Equation B: N2(g) + O2(g) → 2NO(g) DHB = 180.6 kJ

PLAN: Manipulate Equations A and/or B (and their DH values) to get

to the target equation and its DH. Remember: all substances
except those in the target equation must cancel.

72
Using Hess’s Law to Calculate an Unknown DH
CHM135, part 3

PROBLEM: CO(g) + NO(g) → CO2(g) + ½N2(g) DH = ?

Given:
Equation A: CO(g) + ½ O2(g) → CO2(g) DHA = -283.0 kJ
Equation B: N2(g) + O2(g) → 2NO(g) DHB = 180.6 kJ
SOLUTION:

73
Standards Make it Possible to Create DH Databases
CHM135, part 3

Hess’ Law is useful, but to construct and maintain a really useful

database of thermochemical steps, another concept is key:
Standard States
With this, we can usefully
• tabulate Standard Enthalpies of Formation (∆𝑯𝒐𝒇 ) and
• use these to calculate and compare to Standard Enthalpies of
Reaction (∆𝑯𝒐𝒓𝒙𝒏 )

74
 CHM135, part 3
Thermodynamic Standard States
• Thermodynamic values, such as DH, depend on how the reaction is
reported.
H2O (l) → H2O (g) DH = 44 kJ
4 H2O (l) → 4 H2O (g) DH = 176 kJ

C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) DH = –2219 kJ

C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) DH = –2043 kJ

• In order to compare, study and manipulate reactions in a

meaningful way, it is helpful to define a standard set of conditions.
These are called the “standard state.”
75
 CHM135, part 3
Thermodynamic Standard State
• Standard States (according to Chemists):
• pure substance: most stable form at 1 atm and 25 ˚C
• gas: 1 atm and ideal behavior and 25 ˚C
• substance in aqueous solution: 1 M conc. and 25 ˚C
• Standard states are indicated by a superscript ° after the symbol of
the quantity reported.
• Standard enthalpy of reaction is indicated by the symbol DH°rxn. Its
use indicates that the reaction was measured at the standard state.
Thus, all reactants and all products are in their standard state.

76
 CHM135, part 3

Standard Enthalpies of Formation (DH°f)

• The concept of formation equations, and the associated
Standard Enthalpies of Formation (DH°f), provides scientists
with a useful shorthand to tabulate and keep track of enthalpies
of different molecules.
DH°f is also called the “standard heat of formation.”
• DH°f is the enthalpy change for the formation of 1 mole of
substance in its standard state from its constituent elements in
their standard states.
For example: the formation equation for methane is:
C (s) + 2H2 (g) → CH4 (g) DH˚f = -74.8 kJ
and for sodium chloride:
Na (s) + ½ Cl2 (g) → NaCl (s) DH˚f = - 411 kJ
77
 CHM135, part 3
Formation Equations: Practice
• Standard Enthalpies of Formation (DH°f): The enthalpy change
for the formation of 1 mole of substance in its standard state
from its constituent elements in their standard states.
H2(g) + 1/2 O2(g) → H2O(l) DH°f = –286 kJ/mol
3/ H (g)
2 2 + 1/2 N2(g) → NH3(g) DH°f = –46 kJ/mol

2 C(s) + H2(g) → C2H2(g) DH°f = +227 kJ/mol

2 C(s) + 3 H2(g) + 1/2 O2(g)→ C2H5OH(g) DH°f = –235 kJ/mol

O2(g) → O2(g) DH°f = 0

Note that DH°f for any element in its standard state must necessarily be zero,
because the products and reactants are the same in the formation equation.
78
 CHM135, part 3
Selected Standard Enthalpies of Formation at 25°C (298 K)
Formula DH°f (kJ/mol) Formula DH°f (kJ/mol) Formula DH°f (kJ/mol)
• Appendix B of the
Calcium Silver
Ca(s) 0
Cl2(g) 0 text tabulates many
Ag(s) 0
CaO(s) -635.1 HCl(g) -92.3
AgCl(s) -127.0 DH°f ‘s.
CaCO3(s) -1206.9 Hydrogen
H(g) 218 Sodium Other excellent resources are
Carbon
H2(g) 0 Na(s) 0 the thermochemistry data
C(graphite) 0
C(diamond) 1.9 Nitrogen Na(g) 107.8 available in the NIST (National
CO(g) -110.5 N2(g) 0 NaCl(s) -411.1 Institutes of Standards and
CO2(g) -393.5 NH3(g) -45.9 Technology) Chemistry
Sulfur
CH4(g) -74.9 NO(g) 90.3 webbook:
S8(rhombic) 0
CH3OH(l) -238.6 S8(monoclinic) 0.3 https://webbook.nist.gov/chemi
Oxygen
HCN(g) 135 SO2(g) -296.8 stry/
O2(g) 0
CSs(l) 87.9 and Argonne National Lab’s
O3(g) 143 SO3(g) -396.0
active thermochemical tables:
Chlorine H2O(g) -241.8
Cl(g) 121.0 https://atct.anl.gov/Thermoche
H2O(l) -285.8
mical%20Data/
79
Determining DHrxn° from DHf° of Reactants and Products
CHM135, part 3

We can use our database of DHf˚’s to calculate DHrxn˚:

DH°rxn = DH°f (Products) – DH°f (Reactants)
Remember that since DH scales with amount (i.e., it is an extensive
property), the heat of formation of each reactant or product must be
multiplied by its stoichiometric coefficient in the balanced rxn equation.
Thus, for the generalized reaction:
aA + bB → cC + dD
DH°rxn = [cDH°f(C) + dDH°f(D)] – [aDH°f(A) + bDH°f(B)]
Or, using the text’s notation:
DH°rxn = SmDH°f (Products) – SnDH°f (Reactants)
sum of all amount (stoichiometric coefficients)80
Determining DHrxn° from DHf° of Reactants and Products
CHM135, part 3

We can use our database of DHf˚’s to calculate DHrxn˚:

DH°rxn = SmDH°f (Products) – SnDH°f (Reactants)
Why is this?
Conceptually, the above is equivalent to two step process:
1) decomposing the reactants {DHstep1 = -DH°f (Reactants)} into their
constituent elements (in the standard state) and
2) forming the products {DHstep2 = +DH°f (Products)} from these elements.
If the overall reaction is exothermic in the standard state:
H°f (elements)
Decomposition in their standard states In other words, this is a
of reactants
Enthalpy

H°f (reactants) consequence of enthalpy

Formation being a state function – it
of products DH°rxn is equivalent to Hess’s law
H°f (products) 81
 CHM135, part 3
Sweet Application: Glucose in Plants
• Calculate DH° (in kJ) for the photosynthesis of
glucose (C6H12O6) from CO2 and liquid water, a
reaction carried out by all green plants. The heat of
formation of glucose is -1273 kJ/mol.
6 CO2 (g) + 6 H2O (l) → C6H12O6 (s) + 6 O2 (g)
 CHM135, part 3
Fuels and Heats of Combustion
The amount of energy released on burning a substance is called its heat of
combustion, DHoc.
C6H4O6 (s) +6 O2 (g) → 6 CO2(g) + 6 H2O (l) DHoc= -2803 kJ/mol

Thermochemical Properties of Some Fuels 1) Which of these fuels

do you think is used in
rocket engines? Why?

2) Do you think we are

being cheated when we
buy gasoline (a mixture
of octane and toluene)
with 10% ethanol?
cars (Note that you pay for
gas by volume) 83
Where Does DHrxn come from (or go to?)
CHM135, part 3

If energy is exchanged (e.g., heat produced or consumed)

in a chemical reaction, where did that energy come from?

Silberberg Text, section 9.4

donut + 2O2(g) → small hydrocarbons + heat 84

Where Does DHrxn come from (or go to?)
CHM135, part 3

If energy is exchanged (e.g., heat produced or consumed) in a

chemical reaction, where did that energy come from?
E.g., the combustion of methane:
CH4(g) + 2O2(g) → CO2 (g) + 2H2O (g) + heat

The bond energy! The heat released or absorbed during a

chemical change is due to differences between reactant and
product bond energies (BE).
Breaking bonds costs (requires) energy.
Forming bonds liberates (gives off) energy. 85
 Using Bond Energies (BE) to Estimate DH°rxn
CHM135, part 3

DH˚rxn can be approximated by accounting for bonds broken and formed:

DHrxno ≈ BE (reactant bonds) – BE (product bonds)
In this reaction, the
energy required to
break the reactant
bonds (four C-H and two
O-O bonds) is less than
Enthalpy

the energy released

upon the formation of
the product bonds (two
C=O and four H-O
PRODUCTS bonds.) The leftover
(2 C=O and 4 O-H bonds)
energy becomes heat.
86
Using Bond Energies (BE) to Estimate DH°rxn
CHM135, part 3

DH˚rxn can be approximated by accounting for bonds broken and

formed:
DHrxno ≈ BE (reactant bonds) – BE (product bonds)
Conceptually, the above is equivalent to two step process:
1) decomposition of the reactants into atoms and
2) formation of the products from these atoms.

In other words, this is

similar to Hess’s law
Enthalpy

Note: I have included the minus sign

explicitly in the equation above. The
reactants
DH°rxn products
presentation here is thus slightly
different from section 9.4 of the text,
but the net result is the same.87
 Using Bond Energies (BE) to Estimate DH°rxn
CHM135, part 3

Average Bond Energies (BE) in kJ/mol (see also table 9.2 in text) Table shows the average
amount of energy that is
liberated when a bond of
this type is formed.
Note – these tabulated
BE’s are averages (not
exact!) for particular types
of bonds, often tabulated
from gas-phase reactions
under standard conditions.
EXAMPLE: Estimate DH°rxn for Cl2 + H2 → 2 HCl

88
 CHM135, part 3
To Summarize:
A2 + 2B → C2 DH = ? Three ways to calculate:

(1) If you know DH of intermediate reactions, Hess’s Law

DH1 = 1 kJ A2 + 2B → D
DH2 = 2 kJ + D → C2
A2 + 2B → C2 DH = DH1 + DH2 = 3 kJ
(2) Enthalpies of Formation
DHf(A2) = 2 kJ
DHf(B) = 1 kJ DH = DHf(C2) – [DHf(A2) + 2×DHf(B)] = 3 kJ
DHf(C2) = 7 kJ

(3) Bond Energies

BE(A-A) = 6 kJ DH ≈ BE(A-A) – BE(C-C) = 3 kJ
BE(C-C) = 3 kJ
89