Chapter 17

“Thermochemistry”

Pre-AP Chemistry
Charles Page High School
Stephen L. Cotton
 Section 17.1
The Flow of Energy – Heat and Work
 OBJECTIVES:

• Explain how energy,

heat, and work are
related.

2
 Section 17.1
The Flow of Energy – Heat and Work
 OBJECTIVES:

• Classify processes as
either exothermic or
endothermic.

3
 Section 17.1
The Flow of Energy – Heat and Work
 OBJECTIVES:

• Identify the units used to

measure heat transfer.

4
 Section 17.1
The Flow of Energy – Heat and Work
 OBJECTIVES:

• Distinguish between heat

capacity and specific heat
capacity (also called
simply specific heat).
5
 Energy Transformations
 “Thermochemistry” - concerned with
heat changes that occur during
chemical reactions
 Energy - capacity for doing work or
supplying heat
• weightless, odorless, tasteless
• if within the chemical substances-
called chemical potential energy
6
 Energy Transformations
 Gasoline contains a significant
amount of chemical potential energy
 Heat - represented by “q”, is energy
that transfers from one object to
another, because of a temperature
difference between them.
• only changes can be detected!
• flows from warmer  cooler object
7
Exothermic and Endothermic
Processes
 Essentially all chemical
reactions and changes in
physical state involve
either:
a) release of heat, or
b) absorption of heat
 Exothermic and Endothermic
Processes
 Instudying heat changes, think of
defining these two parts:
• the system - the part of the
universe on which you focus your
attention
• the surroundings - includes
everything else in the universe
 Exothermic and Endothermic
Processes
 Together, the system and it’s
surroundings constitute the
universe
 Thermochemistry is concerned
with the flow of heat from the
system to it’s surroundings, and
vice-versa.
Exothermic and Endothermic
Processes
 The Law of Conservation of
Energy states that in any
chemical or physical process,
energy is neither created nor
destroyed.
• All the energy is accounted for
as work, stored energy, or heat.
Exothermic and Endothermic Processes
 Heat flowing into a system from it’s
surroundings:
• defined as positive
• q has a positive value
• called endothermic
–system gains heat (gets
warmer) as the surroundings
cool down
Exothermic and Endothermic Processes
 Heat flowing out of a system into it’s
surroundings:
• defined as negative
• q has a negative value
• called exothermic
–system loses heat (gets cooler)
as the surroundings heat up
 Exothermic and Endothermic
 Fig. 17.2, page 506 - on the left, the
system (the people) gain heat from
it’s surroundings (the fire)
• this is endothermic (q is positive)
 On the right, the system (the body)
cools as perspiration evaporates,
and heat flows to the surroundings
• this is exothermic (q is negative)
 Exothermic and Endothermic
 Every
reaction has an energy
change associated with it
 ** Gummy Bear Sacrifice **
 Exothermic reactions release energy,
usually in the form of heat.
 Endothermic reactions absorb
energy
 Energy is stored in bonds between
atoms
15
 Units for Measuring Heat Flow
1) A calorie is defined as the quantity of
heat needed to raise the temperature
of 1 g of pure water 1 oC.
• Used except when referring to food
• a Calorie, (written with a capital C),
always refers to the energy in food
• 1 Calorie = 1 kilocalorie = 1000 cal.

16
Units for Measuring Heat Flow
2) The calorie is also related to the Joule,
the SI unit of heat and energy
• named after James Prescott Joule
• 4.184 J = 1 cal
 Heat Capacity - the amount of heat
needed to increase the temperature of
an object exactly 1 oC
• Depends on both the object’s mass
and its chemical composition
17
 Heat Capacity and Specific Heat
 Specific Heat Capacity (abbreviated
“C”) - the amount of heat it takes to
raise the temperature of 1 gram of the
substance by 1 oC
• often called simply “Specific Heat”
• Note Table 17.1, page 508 (next slide)
has a HUGE value, when it is
 Water

compared to other chemicals

18
Table of Specific Heats Note the
tremendous
difference in
Specific
Heat.
Water’s
value is
VERY HIGH.
 Heat Capacity and Specific Heat
 For water, C = 4.18 J/(g oC) in
Joules, and C = 1.00 cal/(g oC) in
calories.
 Thus, for water:
• it takes a long time to heat up, and
• it takes a long time to cool off!
 Water is used as a coolant!
• Note Figure 17.4, page 509
20
 Heat Capacity and Specific Heat
 To calculate, use the formula:
q = mass (in grams) x T x C
 heat is abbreviated as “q”
 T = change in temperature
 C = Specific Heat

• Units are either: J/(g oC) or cal/

(g oC)
21
- Page 510
 Section 17.2
Measuring and Expressing
Enthalpy Changes
 OBJECTIVES:

• Describe how
calorimeters are used to
measure heat flow.
23
 Section 17.2
Measuring and Expressing
Enthalpy Changes
 OBJECTIVES:

• Construct
thermochemical
equations.
24
 Section 17.2
Measuring and Expressing
Enthalpy Changes
 OBJECTIVES:

• Solve for enthalpy

changes in chemical
reactions by using heats
of reaction.
25
 Calorimetry
 Calorimetry - the measurement of the
heat into or out of a system for
chemical and physical processes.
• Based on the fact that the heat
released = the heat absorbed
 The device used to measure the
absorption or release of heat in
chemical or physical processes is
called a “Calorimeter”
 Calorimetry
 Foam cups are excellent heat
insulators, and are commonly used as
simple calorimeters under constant
pressure. (They are good because they are well-insulated.)
• Fig. 17.5, page 511
• What about a Dewar’s flask?
 For systems at constant pressure, the
“heat content” is the same as a
property called Enthalpy (H) of the
system
 A foam cup
calorimeter –
here, two
cups are
nestled
together for
better
insulation
 Calorimetry
 Changes in enthalpy = H
 q = H These terms will be used
interchangeably in this textbook
 Thus, q = H = m x C x T
 H is negative for an exothermic
reaction
 H is positive for an endothermic
reaction
 Calorimetry
 Calorimetryexperiments can be
performed at a constant volume
using a device called a “bomb
calorimeter” - a closed system

• Used by nutritionists to measure

energy content of food
A bomb calorimeter

A Bomb Calorimeter
http://www.chm.davidson.edu/ronutt/che115/Bomb/Bomb.htm
- Page 513
Energy C + O2 → CO2 + 395 kJ

C + O2

395kJ
given
off
CO2

Reactants  Products
33
 Exothermic
The products are lower in
energy than the reactants
Thus, energy is released.
ΔH = -395 kJ
• The negative sign does not
mean negative energy, but
instead that energy is lost.
34
 CaCO
CaCO
Energy
3 + 176
3 → CaO
kJ → + CO
CaO +2 CO2

CaO + CO2

176 kJ
absorbed
CaCO3

Reactants  Products
35
 Endothermic
The products are higher in
energy than the reactants
Thus, energy is absorbed.
ΔH = +176 kJ

• The positive sign means

energy is absorbed
36
 Chemistry Happens in
MOLES
 An equation that includes energy is
called a thermochemical equation
 CH4 + 2O2  CO2 + 2H2O + 802.2 kJ

• 1 mole of CH4 releases 802.2 kJ

of energy.
• When you make 802.2 kJ you
also make 2 moles of water
37
 Thermochemical Equations
 Theheat of reaction is the heat
change for the equation, exactly
as written
• The physical state of reactants
and products must also be given.
• Standard conditions (SC) for the
reaction is 101.3 kPa (1 atm.) and
25 oC (different from STP)
38
1 CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l) + 802.2 kJ
 If 10. 3 grams of CH4 are burned completely,
how much heat will be produced?

Convert to moles Convert moles to desired unit

Start with known value

10. 3 g CH4 1 mol CH4 802.2 kJ

16.05 g CH4 1 mol CH4

Ratio from balanced equation

= 514 kJ
ΔH = -514 kJ, which means the heat is
released for the reaction of 10.3 grams CH 4
39
- Page 516
Summary, so far...
 Enthalpy
 The heat content a substance has at a
given temperature and pressure
• Can’t be measured directly because
there is no set starting point
 The reactants start with a heat content
 The products end up with a heat content
 So we can measure how much enthalpy
changes

42
 Enthalpy
 Symbol is H
 Change in enthalpy is H (delta H)
 If heat is released, the heat content of
the products is lower
H is negative (exothermic)
 If heat is absorbed, the heat content
of the products is higher
H is positive (endothermic)
43
Energy

Change is down
ΔH is <0
= Exothermic
(heat is given off)

Reactants  Products
44
Energy

Change is up
ΔH is > 0
= Endothermic
(heat is absorbed)

Reactants  Products
45
 Heat of Reaction
 The heat that is released or absorbed in a
chemical reaction
 Equivalent to H
 C + O2(g)  CO2(g) + 393.5 kJ
 C + O2(g)  CO2(g) H = -393.5 kJ
 In thermochemical equation, it is important
to indicate the physical state
a) H2(g) + 1/2O2 (g) H2O(g) H = -241.8 kJ
b) H2(g) + 1/2O2 (g) H2O(l) H = -285.8 kJ
46
 Heat of Combustion
 The heat from the reaction that
completely burns 1 mole of a
substance:
 C + O2(g)  CO2(g) + 393.5 kJ
 C + O2(g)  CO2(g) H = -393.5 kJ
 NoteTable 17.2, page 517
 DVD: The Thermite Reaction
47
 Section 17.3
Heat in Changes of State
 OBJECTIVES:

• Classify the enthalpy change

that occurs when a substance:
a) melts, b) freezes, c) boils,
d) condenses, or e) dissolves.

48
 Section 17.3
Heat in Changes of State
 OBJECTIVES:

• Solve for the enthalpy change

that occurs when a substance:
a) melts, b) freezes, c) boils,
d) condenses, or e) dissolves.

49
 Heat in Changes of State
1. Molar Heat of Fusion (Hfus.) = the heat
absorbed by one mole of a substance in
melting from a solid to a liquid
q = mol x Hfus. (no temperature change)
Values given in Table 17.3, page 522
2. Molar Heat of Solidification (Hsolid.) = the
heat lost when one mole of liquid
solidifies (or freezes) to a solid
q = mol x Hsolid. (no temperature change)
50
 Heat in Changes of State
 Note:You may also have the
value of these equations as:
q = mass x H

This is because some textbooks

give the value of H as kJ/gram,
instead of kJ/mol
51
 Heat in Changes of State
 Heat absorbed by a melting solid
is equal to heat lost when a
liquid solidifies
• Thus, Hfus. = -Hsolid.
 Note Table 17.3, page 522 for the
number values. Why is there no value
listed for the molar heat of solidification?

52
- Page 521
Heats of Vaporization and Condensation
 When liquids absorb heat at their
boiling points, they become vapors.
3. Molar Heat of Vaporization (Hvap.)
= the amount of heat necessary to
vaporize one mole of a given liquid.
q = mol x Hvap. (no temperature change)
 Table 17.3, page 522
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 Heats of Vaporization and Condensation

 Condensation is the opposite of

vaporization.
4. Molar Heat of Condensation (Hcond.) =
amount of heat released when one mole
of vapor condenses to a liquid
q = mol x Hcond. (no temperature change)
 Hvap. = - Hcond.

55
 Heats of Vaporization and Condensation
 Lets look at Table 17.3, page 522…
 The large values for water Hvap. and
Hcond. is the reason hot vapors such as
steam are very dangerous!
• You can receive a scalding burn from
steam when the heat of condensation
is released!
H20(g)  H20(l) Hcond. = - 40.7kJ/mol
56
-Page 524
 120
The liquid is boiling at 100 C; no temperature change
o

(use q = mol x ΔHvap.)

The gas temperature is rising

from 100 to 120 oC
The Heat Curve for Water, going
(use fromx -20
q = mol ΔT xtoC)120 oC,
similar to the picture on page 523
The liquid temperature is rising
from 0 to 100 oC
(use q = mol x ΔT x C)

The solid is melting at 0o C; no temperature change

(use q = mol x ΔHfus.)
The solid temperature is rising from -20 to 0 oC (use
q = mol x ΔT x C)

58
 Heat of Solution
 Heat changes can also occur when a
solute dissolves in a solvent.
5. Molar Heat of Solution (Hsoln.) = heat
change caused by dissolution of one
mole of substance
q = mol x Hsoln. (no temperature change)
 Sodium hydroxide provides a good
example of an exothermic molar heat of
solution (next slide)
59
 Heat of Solution
H2O(l)
NaOH(s)  Na1+(aq) + OH1-(aq)

Hsoln. = - 445.1 kJ/mol

 The heat is released as the ions
separate (by dissolving) and
interact with water, releasing 445.1
kJ of heat as Hsoln.
• thus becoming so hot it steams!
60
- Page 526
 Section 17.4
Calculating Heats of Reaction
 OBJECTIVES:

• State Hess’s Law of Heat

Summation, and describe
how (or why) it is used in
chemistry.
63
 Section 17.4
Calculating Heats of Reaction
 OBJECTIVES:

• Solve for enthalpy

changes by using Hess’s
law or standard heats of
formation.
64
 Hess’s Law Germain Henri Hess
(developed in 1840) (1802-1850)

 Ifyou add two or more

thermochemical equations to give
a final equation, then you can
also add the heats of reaction to
give the final heat of reaction.

Called Hess’s Law of Heat Summation

65
 How Does It Work?
1) If you turn an equation around, you change
the sign:
If H2(g) + 1/2 O2(g) H2O(g) H=-285.5 kJ
then the reverse is:
H2O(g) H2(g) + 1/2 O2(g) H =+285.5 kJ
2) If you multiply the equation by a number,
you multiply the heat by that number:
2 H2O(g) H2(g) + O2(g) H =+571.0 kJ
3) Or, you can just leave the equation “as is”
66
 Hess’s Law - Procedure Options:
1. Use the equation as written
2. Reverse the equation (and
change heat sign + to -, etc.)
3. Increase the coefficients in the
equation (and increase heat by
same amount)
 Note samples from pages 528 and 529
67
 Standard Heats of Formation
 The H for a reaction that produces (or
forms) 1 mol of a compound from its
elements at standard conditions
 Standard conditions: 25°C and 1 atm.
 Symbol is: H
0
f
The standard heat of formation of
an element in it’s standard state is
arbitrarily set at “0”
This includes the diatomic elements
68
 Standard Heats of Formation
 Table 17.4, page 530 has standard heats
of formation
 The heat of a reaction can be calculated
by:
• subtracting the heats of formation of
the reactants from the products
Ho = (H 0f Products) - (H 0f Reactants)
Remember, from balanced equation: Products - Reactants
69
- Page 531
 Another Example
 CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(g)
0
H f CH (g) = - 74.86 kJ/mol
4
0
H f O (g) = 0 kJ/mol (Because it is an element)
2
0
H f CO (g) = - 393.5 kJ/mol
2
0
H f H O(g) = - 241.8 kJ/mol
2
H= [-393.5 + 2(-241.8)] - [-74.86 +2 (0)]
H= - 802.24 kJ (endothermic or exothermic?)
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72