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Thermochemistry
Heat, work, state func8ons,
calorimetry, and other things you can
warm to!

What is energy?
Standard deni8on:

Energy is the ability [capacity] to to work.

What does this mean?

NOTHING!

A More Abstract Set of Deni8ons

Mechanics
Kine%c Energy:
The energy of an object in
mo8on.

E = mv2

Poten%al Energy:

Stored energy.
Results from the presence of a
force eld.

Thermodynamics
Heat:
Once thought to be a separate
form of energy but now known
to result from the mo8on of
par8cles.

Work:
This can be either mechanical
(give example) or nonmechanical
(give example).

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The Law of Conserva8on of Energy

Energy can neither be created nor destroyed.

Energy can only be transferred from one object to
another.

The total energy of a closed system is constant.
This leads eventually to the First Law of
Thermodynamics!

Rening this...
Energy transfer occurs between a system and its
surroundings.

So, for a closed system, this transfer is from one
part of the system to another.

Corollary: The universe isby deni=ona
closed system!

An Illustra8on...

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The basic (SI) unit of energy...

Some other energy units...

The First Law

The internal energy of a system is given by

E = Kine=c Energy + Poten=al Energy.

The internal energy is a state func%on.

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State Func8ons are path independent:

An example below...
Note that more than
one path is possible in
climbing the mountain.
But, the height
dierence is
independent of the
path taken!

Total Energy is a State Func%on!

We shall show this in the next two slides by
looking at a chemical reac8on in two direc8ons:

C(s) + O2(g) CO2(g)

CO2(g) C(s) + O2(g)

C(s) + O2(g) CO2(g)

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CO2(g) C(s) + O2(g)

In general...

Heat and Work...

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Conven8ons...
q > 0: Heat added to system
q < 0: System gives up heat

w > 0: Work done on system
w < 0: The system does work (on surroundings)

How do we know that heat is energy?

The rst suspicion that
heat is a form of energy
was from Count Rumford
(Benjamin Thompson).

You have probably all seen
his picture...

A note about Count Rumford...

He was an American.
He spied for the Bri8sh
during the Revolu8on and
had to ee.
He did military
engineering for the Holy
Roman Empire during
which he noted the heat
produced in boring
cannons.
He was rewarded by
being made a Count.

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He married the widow of Lavoisier...

Lavoisier was important
in that he essen8ally
discovered the concept
of mass conserva8on.
Here he is with his
wife...

Lavoisier was a great scien8st!

His inven8on of the
analy8cal balance lead
to being able to
quan8fy maier.
The French gave him
the following reward...

Of course, they were immediately

sorry and made many statues of him...

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This statue probably best sums up

what Lavoisier thought about this...

The proof that heat is a form of

energy...
This came about from the
work of James P. Joule.
He was a very wealthy
Sco<sh gentleman
scien8st.
He owned a large
brewery/dis8llary and
had lots of 8me and
money!
He is to the right...

Joules Apparatus
Joule was an ingenious
inventor and a superb
designer of scien8c
apparatus.
He was a major pioneer
of calorimetry.
We shall explain and
discuss his apparatus (at
right)...

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The quan8ca8on of heat...

We look at heat rst
(work comes soon!).
In general, the amount
of heat entering or
leaving a system is
propor8onal to the
systems change in
temperature.
We show this to the
right...

C is called the heat capacity.

For the general case we
just gave (simply calling
it C ), this is just the
system heat capacity.
We can rearrange our
equa8on to give the
deni8on in a clearer
form.
We do this now

The Specic Heat Capacity

It is more useful if we
dene the heat capacity
for a unit mass of a
substance.
This gives the specic
heat capacity.
This is also oqen
shortened to specic
heat.

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Some Typical Specic Heat Capaci8es

We list a few to the
right.
Note that these are
dened at 298K (25C).
Heat capaci8es do
change with
temperature!
Why? (Think in terms
of atoms-rst!)

Molar Heat Capaci8es

We give these for the
sake of completeness.
The dening equa8ons
are to the right.
We dene these to give
the heat measure at
constant volume and at
constant pressure,
respec8vely.

A Special Case for CP

Dulong

Pe5t

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Here are Cs of some metals...

Lets get the molar heat capaci8es (CP)

So, if we mul8ply by the atomic

weights of the metals, we get...

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These numbers are almost the same!

In fact, for a given metal,

CP 3R

(R = 8.314472 J/molK)

An applica8on: Measuring the heat

capacity of a metal
This is a very simple trick
used with a piece of metal
and water.
The metal is usually
transferred from boiling
water (100C) to colder
water (e.g., 25C).
If we know the masses of
the water and the metal
and we measure the nal T,
we can get Cs of the metal.
The basic idea is to the
right...

What happens during this process?

The metal cools from some temperature (T2)
to a nal temperature (Tf).
The water is warmed from some temperature
(T2) to the same nal temperature (Tf).
We do the math in the next slide!
(Note that this is the same example as in the
book but with a dierent quan8ty being
found!)

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Here is the math!

We do an example (adapted from Tro)

32.5 g of aluminum
ini8ally at 45.80C are
immersed in 105.3 g of
water ini8ally at 15.40C.
The nal temperture is
found to be 17.30C.

Calculate the specic heat
capacity of aluminum.

A general formula for the example in

the book...

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Same thing (numbers added)...

Intermission...
We shall look at heat transfer further.
This will involve calorimetry.
But rst it would be wise to look at WORK!

Quan8fying work...
The simplest form of work is given by a force
ac8ng over a distance:

w = Force Distance

{ 1J = 1 Nm = 1 (kgm/s2) m = 1 kgm2/s2 }

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In chemistry, the most common work

is Pressure-Volume work...

Here is the appropriate boring slide!

We must ask a ques8on here!

WHY IS
THERE A
MINUS
SIGN HERE?

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The whole story (for calculus bus)

PV work gives us a new energy unit!

This unit is the liter-
atmosphere.

1 Latm = 101.325 J

Note that this is an exact
conversion factor!

Deriva8on

A very special case...

At constant volume, we have V = 0.

So, w = -PV = 0.

Thus, E = q + w = q qV.

(At constant volume, the internal energy change
is just the heat of the process!)

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This is useful in bomb calorimetry

Volume not constant

Volume Constant

Bomb Calorimetry & Heat of

Combus8on

The Heat of Combus8on (constant V) is

obtained as follows:

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Example
1.550 g of hexane (C6H14,
86.17 g /mol) undergo
combus8on in a bomb
calorimeter (with Ccal =
5.73 kJ/K. The
temperature increases
from 25.87C to 38.13C.

Calculate E (kJ/mol) for
the combus8on of hexane.

Some comments...
Calorimeters need to be calibrated.
This is done either by
running a known electric current through a known
resistance or
burning rst a standard substance (most common
are benzoic acid, naphthalene, or sucrose).

Tabulated heats of combus8on are corrected

to constant Pressure to get the Enthalpy of
combus8on.

Enthalpy! (H)
At constant volume, q = E = qV.

This is useful, BUT

most chemical reac8ons are run at constant
pressure!

How do we get around this?

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Enthalpy to the rescue!

We dene a new func8on: H = E + PV

At constant pressure: H = E + PV

Then, lets plug in what we know:

H = E + PV = (qP + w) + PV = qP + w w = qP

This is a state func8on.

So, now we have TWO state func8ons!

These are both equal to
the heat of a process
under special
condi8ons.
Later on, we shall see
even more state
func8ons!
Be sure to know what
we show to the right!

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Actually, we have three!

PV is also a state
func8on!

(Why?)

Further discussion...
E is all the energy exchanged between a
system and its surroundings.
H is simply the heat exchanged at constant
pressure.
For liquids and solids, E H. (Why?)
Most of the 8me, it is H that we experience.

Some new terms...

Endothermic

Exothermic

Heat goes into the system.

Heat leaves the system.

H > 0.

H < 0.

(These would feel cold to

you. Why?)

(These would feel warm to

you. Why?)

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Two Other Useful Terms...

Adiaba5c


For this, q = 0.

For such systems, E = w.

Istothermal


This is a very special case!

T = 0

Stoichiometry and H
If all we ever did was burn a single mole of
substance, life would be easy.
However, more oqen than not, we need to
know H for a given number of grams, kg,
pounds, or moles of a substance.
This is done in the book but we shall give the
examples using an alternate method.

An example...
An LP gas tank in a home barbeque contains
13.2 kg of propane, C3H8. Calculate the heat (in
kJ) associated with the complete combus8on of
the propane.

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We start with a BCE (balanced

chemical equa8on)...

Next, we set this up (as we would in a

spreadsheet)...

And we solve (pung in unit

conversions as needed)...

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This is mathema8cally equivalent to

the way the book did it!

Lets do another one!

(This is kind of addic8ve...)
What mass of butane (g) is necessary to produce
1500 kJ of heat?

What mass of CO2 is produced?

All this on the next slide!

Eureka!

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Constant Pressure Calorimetry

H is used much more
oqen than E since most
processes run at constant
P.

A primi8ve constant
pressure calorimeter is the
familiar coee-cup
calorimeter...

For a Constant-Pressure Calormeter

A few details here...

We have to look at this in terms of individual
processes.
For instance, if a reac8on occurs in water, we
need to treat the total heat exchange in terms
of its individual components.
This is easily done if we rememberand think
in terms ofthe First Law.

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An Example...
The addi8on of HCl(aq) to a silver nitrate (aq) solu8on
precipitates AgCl according to

AgNO3(aq) + HCl(aq) AgCl(s) + HNO3(aq)

50.0 mL of 0.100M AgNO3 + 50.0 mL 0.100M HCl react
stoichiometrically and T changes from 23.40C to 24.21C.

Calculate H (kJ/mol(AgCl)) for the reac8on as wriien.

I shall explain the logic to the

following steps verbally as we go!

First, note this:

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Finishing Up...
The amount of heat
depends upon the amount
of substance used or
formed.

For our par8cular case...

For the reac8on, as wriien...

Some special points about H

H is an extensive func8on.
H is independent of path but
does depend on the ini8al and nal state (i.e.,
the direc8on of a process).
When we write H, we are referring to the
chemical equa8on as wriAen. (This last
statement carries over to rules we now
discuss.)

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Some rules!
1. If a chemical equa8on be mul8plied by some
factor, the Hrxn is also mul8plied by the
same factor.
2. If a chemical reac8on be reversed, then Hrxn
changes sign.
3. If a chemical reac8on can be expressed as the
sum of a series of steps, then Hrxn for the
overall equa8on is the sum of the heats of
reac8on for each step.

This is true for any extensive state

func8on!
All this is is the rst law of thermodynamics.
Here, we are using this with enthalpy.
When we do this, we give this the special case
of Hesss Law.

We look at Hess and an example...

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Take this a liile further...

Book Example

Prac8cal Example: Heat of forma8on

of CO...

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Bringing order into chaos...

There are lots of ways to combine individual
reac8ons to give total reac8ons.
But there is one really ecient way to do this:
Heats of forma8on!

We start with the idea of a standard

state!
Pure substance or 1M solu8on of same

1 atm pressure

25.00C (298.15K)

H is the standard enthalpy change and is
dened for the above condi8ons!

Standard Enthalpy of Forma8on (Hf)

For a pure compound (in its standard state) this
is the change in enthalpy when 1 mole of the
compound forms from its cons8tuent elements
in their standard state.

Hf = 0 (by den8on) for any element in its
standard state.

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For any chemical reac8on...

A Table!

Example
Rather than give a slide, I am going to do an
example on the board.
This is so that you can see the development
and execu8on of the concepts.
The example is this: The combus8on of
ethanol (using numbers from the table just
given).

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AND NOW...

pHun stu
just for
YOU!
(get ready!)

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