Chapter 5

Thermochemistry

Energy
Types of energy
Kinetic
Potential
Gravitational
Electrostatic
Chemical

Measured in joules (J), or calories (cal)

1 cal = 4.184 J

Systems and Surroundings

The system is what we are studying
The surroundings are everything else
Universe = system + surroundings
Types of systems
Closed - common in chemistry
Exchanges energy but not mass with
surroundings

What Energy Can Do

Energy can be gained by a system if:
Work is done on the system
Heat is gained by the system

Energy can be lost by a system if:

The system does work
The system loses heat

So, what is work?

For that matter, what is heat?

Whos Doing The Work?

Question
If a student compresses a gas by pushing
down on a piston:
a. The student has done work on the system;
energy of the system decreases
b. The system has done work on the student;
energy of the system decreases
c. The student has done work on the system;
energy of the system increases
d. The system has done work on the student;
energy of the system increases

First Law of Thermodynamics

Energy can neither be created nor
destroyed
An easier way to say this:
Energy is conserved

An even easier way to say this:

YOU CANT WIN!

What Does This Mean?

Internal energy is the energy of a system (E)
If a system changes its energy, the new
energy is:
E = Efinal - Einitial
E is negative if system has lost energyto?
The surroundings!

E is positive if system has gained

energyfrom?
The surroundings!

Put Another Way

Chemical Reactions and

Energy

E, Heat, and Work

Systems and surroundings may exchange
energy as
Heat
Work

E = q + w
q = heat
+q is heat GAINED by system, -q is heat LOST by
system

w = work
+w is work done ON system, -w is work done BY system

Example
What is the E for a system for a
process in which the system absorbs
140 J of heat from the surroundings,
and does 85 J of work on the
surroundings?

Heat
Endothermic (heat in) processes
The system absorbs heat

Exothermic (heat out) processes

The system loses heat

Temperature is proportional to the

internal energy of a system

Exothermic and Endothermic

Processes

State Functions
The total energy (E) for a system is hard
to know
We generally talk about change in energy

Factors influencing E
Temperature
Pressure
Total quantity of matter

State Functions
Properties of systems that are defined
by the systems condition (state) are
state functions
State functions depend upon conditions,
NOT pathway
Internal energy is a state function

Not State Functions

Heat (q) is not a state function
A system can get from one state to another
through loss/gain of various amounts of heat

Work (w) is not a state function

A system can get from one state to another
through doing/being subjected to various amounts
of work

For a given energy change, q and w can vary,

but E does not

Reactions and Work

Most reactions in chemistry are open to
the atmosphere
Pressure is constant

Work is associated with a change in

volume

Question
Which of the following represents the
relationship between system and
surroundings energy?
a.
b.
c.
d.

Esystem = Esurroundings
Esystem = -Esurroundings
Esystem = 2(Esurroundings)
Esystem = -2(Esurroundings)

Question
Which of the following defines an
EXOTHERMIC reaction?
a.
b.
c.
d.

-E
+E
-q
+q

Question
Which of the following is a state
function?
a. Internal energy (of a system)
b. Heat
c. Work

PV Work
PV work
Change in gas volume
W = -PV
Expansion: V is positive, work BY system
Compression: V is negative, work ON system

PV Work

An Important Note
Temperature is proportional to the internal
energy of the system
All other factors held constant, temperature
increases if heat (energy) is absorbed
All other factors held constant, temperature
increases if work is done ON system
All other factors held constant, temperature
decreases if work is done BY system

Question
For gas in a piston canister, which of
the following would NOT constitute an
increase in E of the system?
a. Pushing down on the piston
b. Lighting a candle under the canister
c. Pulling up on the piston

Question
If you put your hand on a refrigerator
compressor, how would you expect it
to feel?
a. Hot
b. Cold

Question
What does it mean to say temperature of a
system is proportional to E?
a. The temperature of the system can be used to
calculate E
b. Comparing the temperatures of different
systems allows you to compare their Es
c. If E for a system is positive, the temperature
will decrease
d. If E for a system is positive, the temperature
will increase

Enthalpy (H)
Provides a quantification of heat flow if
Constant pressure
No work other than PV work
H = E + PV
Internal energy plus product of
pressure/volume
H is a state function

H
H is change in enthalpy
H = (E + PV), or E + PV
Buteasier
In systems at constant pressure, H = q
If H is positive, ENDOTHERMIC reaction
If H is negative, EXOTHERMIC reaction

Enthalpies of Reaction
For a reaction, Hrxn = Hprod - Hreact

Other Enthalpy Issues

What happens if we reverse the
reaction?
Magnitude of Hrxn is the same, sign
changes

What happens if we burn two moles of

methane?
Twice as much heat is evolved

Definition
Squir-rel-y adj. Slang
1.Eccentric.
2.Cunningly unforthcoming or reticent.
The American Heritage Dictionary of the
English Language, Fourth Edition.

Question
A squirrel is sitting on an electrical
wire. What kind of energy does he
have?
a. Gravitational potential
b. Electrical potential
c. Kinetic

Question
The squirrel leaps for a neighboring
wire; as he moves through the air
(quite some distance above the
ground), what kind of energy does he
have?
a. Gravitational potential
b. Kinetic
c. Gravitational potential and kinetic

Calorimetry
How can we measure Hrxn
experimentally?
Need to know a few facts
As substances gain heat, they get hotter (and vice
versa)
Substances increase/decrease in temperature
predictably
Can quantify heat gained/lost based upon temperature
change

Heat Capacity (C)

The amount of heat necessary to raise
temperature of an object by 1 C (1 K)
Larger heat capacity means more heat
required to raise temperature

Molar heat capacity (Cmolar) is heat

capacity of one mole of a substance
Specific heat (s) is heat capacity of one
gram of a substance

Specific Heat (s)

s=

q
m x T

Grams of
substance

Quantity of heat
transferred

Change in
temperature
Can also write in terms of heat:
q = msT

Example
What is the specific heat of water, given
that it takes 418 J of heat to raise the
temperature of 50.0 g by 2.00 K?

Question
By what amount will the temperature of
50.0 g of water change if it absorbs 815
J of heat, given that swater = 4.18 J/gK?

Question
How much does 1 cal of heat affect the
temperature of 1 g of water? (The
specific heat of water is 1 cal/gC)

The Coffee Cup Calorimeter

Not sealed
Reaction occurs at
constant (atm) pressure
Coffee cup is insulating,
has low heat capacity, so
low heat absorption
qsoln = (ssoln)(gsoln)(T) = -qrxn

Example
50.0 mL 0.100 M AgNO3 and 50.0 mL
0.100 M HCl are mixed in a coffee cup
calorimeter. The temperature of the
solution increases from 22.20C to
23.11C; calculate enthalpy of reaction
for the reaction:
AgNO3 (aq) + HCl (aq) AgCl (s) + HNO3 (aq)

Bomb Calorimetry
Combustion in
sealed bomb
Heat absorbed by
contents of
calorimeter
qrxn = -CcalT
Constant volume

Example
A 1.800 g sample of phenol (MW =
94.11 g/mol) was burned in a bomb
calorimeter with a heat capacity of
11.66 kJ/C. The temperature of the
calorimeter and contents increased from
21.36C to 26.37C. What is the heat of
combustion per mole of phenol?

Question
Which has a higher specific heat:
wood or metal?
a. Wood
b. Metal

Question
If a system changes temperature a
LOT for the amount of heat it absorbs,
what kind of specific heat does it have:
a. High
b. Low

Question
In a coffee-cup calorimeter, what do
we assume comprises the system to
SIMPLIFY our calculations?
a. Everything in the universe
b. The cup plus the water in the cup
c. The water in the cup ONLY

Hesss Law
Very formal definition
If a reaction is carried out in a series of
steps, H for the overall reaction will equal
the sum of the Hs for individual steps

What this really means

We can use known H values to determine
unknown H values

Example
Calculate Hrxn for the formation of CO,
given the reactions below:
C(s) + 1/2 O2 (g) CO(g) Hrxn = ?
C(s) + O2 (g) CO2(g) Hrxn = -393.5 kJ
CO(g) + 1/2 O2 (g) CO2(g) Hrxn = -283.0 kJ

Enthalpies of Formation
Hf is enthalpy change for formation of
compound from constituent elements
Depends upon conditions of reactants and
products
Temp, pressure, state

For simplicity, standard state is defined

Standard State
Set of conditions (the ones found in
most laboratories) for which enthalpies
are recorded
Pure form of a substance
Pressure = 1 atm
Temperature = 298K (25C)

H = Enthalpy at Standard
State
Standard enthalpy change
Indicates that all reactants and products
are in standard state conditions
Can be for formation or reaction

Hf
Standard enthalpy of formation
Change in enthalpy for reaction that forms
one mole of compound from elements
All substances in standard state
2 C(graphite) + 3 H2 (g) + 1/2 O2 (g) C2H5OH(l) Hf = -277.7 kJ

Note that all substances are in their most stable form

Table of Hf Values

QuickTime and a
TIFF (Uncompressed) decompressor
are neede d to see this picture.

Question
True or False: to use Hesss Law to
find the enthalpy of reaction, the
reaction MUST have taken place via a
series of steps, for which the
enthalpies of reaction are known.
a. TRUE
b. FALSE

Careful! Tricky question!

Question
For which of the following is the
enthalpy of formation ZERO?
a.
b.
c.
d.

O2(g)
O2(l)
O(g)
All of these

Question
True or False: Because ethane (C2H6)
is most stable as a gas, the enthalpy
of formation of gaseous ethane is
ZERO
a. TRUE
b. FALSE

Example
What is the equation for formation of
glucose in terms of standard enthalpy of
formation?

Enthalpy of Reaction
Enthalpies of formation (Hf) can be
used to calculate standard enthalpy of
reaction (Hrxn)
Hrxn = (sum of Hf of products) - (sum of
Hf of reactants)

Finding Hrxn
Find Hrxn for the combustion of C3H8(g)
in O2(g) via the reaction:
C3H8(g) + 5 O2(g) 3 CO2(g) + 4H2O(l)

Finding Hf
Find Hf for C3H6O(l), given the
equation:
C3H6O(l) + 4 O2(g) 3 CO2(g) + 3 H2O(l), Hrxn = -1790 kJ

Food and Fuel

Combustion is the burning of a chemical
to release heat and produce simpler
substances
Foods are burned in the presence of
oxygen to produce various products
CO2
H2O
Chemical energy or heat

Food Calories
A food Calorie is actually a kcal (1000
cal)
Three types of nutrients
Carbohydrates, 4 Cal/g
Proteins, 4 Cal/g
Fats, 9 Cal/g

Heat IS Energy
The Calories in a meal can be used to
fuel biological processes

Example
A meal consisting of a Double QuarterPounder with Cheese, large fries, and large
Triple-Thick Chocolate Shake contains 2470
food calories. If the energy from this meal
were used to heat 10 gallons (approximately
38L or 38kg) of water initially at room
temperature (25C), how hot would the
water get?