Chapter 7: Thermochemistry

Thermochemistry
Thermodynamics is the science of the
relationship between heat and other forms
of energy.

Thermochemistry is the study of the quantity
of heat absorbed or evolved by chemical
reactions.
Energy
The Law of Conservation of Energy:
Energy may be converted from one form to
another, but the total quantities of energy
remain constant.
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Presentation of Lecture Outlines, 64
Types of Energy
1. Kinetic energy
2. Potential energy
3. Chemical energy
4. Heat energy
5. Electric energy
6. Radiant energy
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Heat of Reaction
In chemical reactions, heat is often
transferred from the system to its
surroundings, or vice versa.
The substance or mixture of substances
under study in which a change occurs is
called the thermodynamic system (or
simply system.)
The surroundings are everything in the
vicinity of the thermodynamic system.
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Heat of Reaction
Heat is denoted by the symbol q.
The sign of q is positive if heat is absorbed by
the system.
The sign of q is negative if heat is evolved by
the system.
Heat of Reaction is the value of q required
to return a system to the given
temperature at the completion of the
reaction.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 7 of 50
Contents
7-1 Getting Started: Some Terminology
7-2 Heat
7-3 Heats of Reaction and Calorimetry
7-4 Work
7-5 The First Law of Thermodynamics
7-6 Heats of Reaction: U and H
7-7 The Indirect Determination of H: Hesss Law
7-8 Standard Enthalpies of Formation


Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 8 of 50
6-1 Getting Started: Some Terminology
System
Surroundings
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 9 of 50
Terminology
Energy, U
The capacity to do work.
Work
Force acting through a distance.
Kinetic Energy
The energy of motion.

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 10 of 50
Energy
Potential Energy
Energy due to condition, position, or
composition.
Associated with forces of attraction or
repulsion between objects.
Energy can change from potential to kinetic.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 11 of 50
Energy and Temperature
Thermal Energy
Kinetic energy associated with random
molecular motion.
In general proportional to temperature.
An intensive property.
Heat and Work
q and w.
Energy changes.

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 12 of 50
Heat
Energy transferred between a system and its
surroundings as a result of a temperature
difference.
Heat flows from hotter to colder.
Temperature may change.
Phase may change (an isothermal process).

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 13 of 50
Units of Heat
Calorie (cal)
The quantity of heat required to change the
temperature of one gram of water by one
degree Celsius.
Joule (J)
SI unit for heat
1 cal = 4.184 J
Energy
The Law of Conservation of Energy:
Energy may be converted from one form to
another, but the total quantities of energy
remain constant.
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16
Heat of Reaction
In chemical reactions, heat is often
transferred from the system to its
surroundings, or vice versa.
The substance or mixture of substances
under study in which a change occurs is
called the thermodynamic system (or
simply system.)
The surroundings are everything in the
vicinity of the thermodynamic system.
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17
Heat of Reaction
Heat is denoted by the symbol q.
The sign of q is positive if heat is absorbed by
the system.
The sign of q is negative if heat is evolved by
the system.
Heat of Reaction is the value of q required
to return a system to the given
temperature at the completion of the
reaction.
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18
Heat of Reaction
An exothermic process is a
chemical reaction or physical
change in which heat is evolved (q
is negative).
An endothermic process is a
chemical reaction or physical
change in which heat is absorbed
(q is positive).
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 19 of 50
Heat Capacity
The quantity of heat required to change the
temperature of a system by one degree.

Molar heat capacity.
System is one mole of substance.
Specific heat capacity, c.
System is one gram of substance
Heat capacity
Mass specific heat.
q = mcT

q = CT

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 20 of 50
Conservation of Energy
In interactions between a system and its
surroundings the total energy remains constant
energy is neither created nor destroyed.
q
system
+ q
surroundings
= 0
q
system
= -q
surroundings

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 21 of 50
Determination of Specific Heat
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 22 of 50
Example 7-2
Determining Specific Heat from Experimental Data.
Use the data presented on the last slide to calculate the specific
heat of lead.
q
lead
= -q
water

q
water
= mcT = (50.0 g)(4.184 J/g C)(28.8 - 22.0)C
q
water
= 1.4x10
3
J
q
lead
= -1.4x10
3
J = mcT = (150.0 g)(c)(28.8 - 100.0)C
c
lead
= 0.13 Jg
-1
C
-1


Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 23 of 50
7-3 Heats of Reaction and Calorimetry
Chemical energy.
Contributes to the internal energy of a system.
Heat of reaction, q
rxn.
The quantity of heat exchanged between a
system and its surroundings when a chemical
reaction occurs within the system, at constant
temperature.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 24 of 50
Heats of Reaction
Exothermic reactions.
Produces heat, q
rxn
< 0.
Endothermic reactions.
Consumes heat, q
rxn
> 0.
Calorimeter
A device for measuring quantities of heat.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 25 of 50
Bomb Calorimeter
q
rxn
= -q
cal

q
cal
= q
bomb
+ q
water
+ q
wires
+
Define the heat capacity of the
calorimeter:
q
cal
= m
i
c
i
T = CT
all i
heat
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 26 of 50
Using Bomb Calorimetry Data to Determine a Heat of Reaction.
The combustion of 1.010 g sucrose, in a bomb calorimeter,
causes the temperature to rise from 24.92 to 28.33C. The
heat capacity of the calorimeter assembly is 4.90 kJ/C.
(a) What is the heat of combustion of sucrose, expressed in
kJ/mol C
12
H
22
O
11

(b) Verify the claim of sugar producers that one teaspoon of
sugar (about 4.8 g) contains only 19 calories.
Example 7-3
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 27 of 50
Example 7-3
Calculate q
calorimeter
:
q
cal
= CT = (4.90 kJ/C)(28.33-24.92)C = (4.90)(3.41) kJ
= 16.7 kJ

Calculate q
rxn
:
q
rxn
= -q
cal
= -16.7 kJ

per 1.010 g
Example 7-3
Heat of Reaction
Exothermicity
out of a system






q < 0
Endothermicity
into a system







q > 0
Energy
System
Surroundings
Energy
System
Surroundings
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 29 of 50
Example 7-3
Calculate q
rxn
in the required units:
q
rxn
= -q
cal
=
-16.7 kJ

1.010 g

= -16.5 kJ/g
343.3 g

1.00 mol

= -16.5 kJ/g
= -5.65 10
3
kJ/mol
q
rxn

(a)
Calculate q
rxn
for one teaspoon:
4.8 g

1 tsp

= (-16.5 kJ/g)( q
rxn

(b)
)(
)= -19 cal/tsp
1.00 cal

4.184 J

Example 7-3
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 30 of 50
Coffee Cup Calorimeter
A simple calorimeter.
Well insulated and therefore isolated.
Measure temperature change.
q
rxn
= -q
cal

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 31 of 50
7-4 Work
In addition to heat effects chemical reactions
may also do work.


Gas formed pushes against
the atmosphere.
Volume changes.

Pressure-volume work.


Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 32 of 50
Pressure Volume Work
w = F d
= (P A) h
= PV
w = -P
ext
V
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 33 of 50
Example 7-3
Assume an ideal gas and calculate the volume change:
V
i
= nRT/P
= (0.100 mol)(0.08201 L atm mol
-1
K
-1
)(298K)/(2.40 atm)
= 1.02 L
V
f
= 1.88 L

Example 7-5
Calculating Pressure-Volume Work.
Suppose the gas in the previous figure is 0.100 mol He at 298 K.
How much work, in Joules, is associated with its expansion at
constant pressure.
V = 1.88-1.02 L = 0.86 L
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 34 of 50
Example 7-3
Calculate the work done by the system:
w = -PV
= -(1.30 atm)(0.86 L)(
= -1.1 10
2
J
Example 7-5
)
101 J

1 L atm

Where did the conversion factor come from?
Compare two versions of the gas constant and calculate.
8.3145 J/mol K 0.082057 L atm/mol K
1 101.33 J/L atm

Hint: If you use
pressure in kPa you
get Joules directly.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 35 of 50
7-5 The First Law of Thermodynamics
Internal Energy, U.
Total energy (potential and kinetic) in a system.

Translational kinetic energy.
Molecular rotation.
Bond vibration.
Intermolecular attractions.
Chemical bonds.
Electrons.

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 36 of 50
First Law of Thermodynamics
A system contains only internal energy.
A system does not contain heat or work.
These only occur during a change in the system.


Law of Conservation of Energy
The energy of an isolated system is constant
U = q + w
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 37 of 50
First Law of Thermodynamics
A system contains only internal energy.
A system does not contain heat or work.
These only occur during a change in the system.


Law of Conservation of Energy
The energy of an isolated system is constant
U = q + w
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38
Enthalpy and Enthalpy Change
The heat absorbed or evolved by a reaction
depends on the conditions under which it occurs.
Usually, a reaction takes place in an open vessel,
and therefore at the constant pressure of the
atmosphere.
The heat of this type of reaction is denoted q
p
,
the heat at constant pressure.
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39




An extensive property is one that depends on the
quantity of substance.
Enthalpy is a state function, a property of a system
that depends only on its present state and is
independent of any previous history of the system,
or independent of path.
Enthalpy and Enthalpy Change
Enthalpy, denoted H, is an extensive property of
a substance that can be used to obtain the heat
absorbed or evolved in a chemical reaction.
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40
The change in enthalpy for a reaction at a
given temperature and pressure (called the
enthalpy of reaction) is obtained by
subtracting the enthalpy of the reactants from
the enthalpy of the products.
) reactants ( (products)
H H H
Enthalpy and Enthalpy Change
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41
The change in enthalpy is equal to the heat
of reaction at constant pressure. This
represents the entire change in internal energy
(U) minus any expansion work done by
the system.
p
q H
Enthalpy and Enthalpy Change
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42

The internal energy of a system, U, is precisely
defined as the heat at constant pressure plus the
work done by the system:

(See Animation: Work vs. Energy Flow)
In chemical systems, work is defined as a change in
volume at a given pressure, that is:
Enthalpy and Internal Energy

w q U
p
V P w
Enthalpy and Enthalpy Change
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43

So H is essentially the heat obtained or absorbed
by a reaction in an open vessel where the work
portion of U is unmeasured.
Since the heat at constant pressure, q
p
,
represents H, then

V P H U
Enthalpy and Enthalpy Change
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44
Thermochemical Equations
A thermochemical equation is the
chemical equation for a reaction (including
phase labels) in which the equation is given
a molar interpretation, and the enthalpy of
reaction for these molar amounts is written
directly after the equation.
kJ -91.8 H ); g ( NH 2 ) g ( H 3 ) g ( N
3 2 2

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45
kJ 483.7 - H ; ) g ( O H 2 ) g ( O ) g ( H 2
o
2 2 2

In a thermochemical equation it is
important to note phase labels because the
enthalpy change, H, depends on the phase
of the substances.
kJ 571.7 - H ; ) l ( O H 2 ) g ( O ) g ( H 2
o
2 2 2

Thermochemical Equations
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 46 of 50
First Law of Thermodynamics
A system contains only internal energy.
A system does not contain heat or work.
These only occur during a change in the system.


Law of Conservation of Energy
The energy of an isolated system is constant
U = q + w
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 47 of 50
First Law of Thermodynamics
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 48 of 50
Changes of State of Matter
H
2
O (l) H
2
O(g) H = 44.0 kJ at 298 K
Molar enthalpy of vaporization:
Molar enthalpy of fusion:
H
2
O (s) H
2
O(l) H = 6.01 kJ at 273.15 K
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 49 of 50
Example 7-3
Example 7-8
Break the problem into two steps: Raise the temperature of
the liquid first then completely vaporize it. The total enthalpy
change is the sum of the changes in each step.
Enthalpy Changes Accompanying Changes in States of Matter.
Calculate H for the process in which 50.0 g of water is
converted from liquid at 10.0C to vapor at 25.0C.

= (50.0 g)(4.184 J/g C)(25.0-10.0)C +
50.0 g

18.0 g/mol

44.0 kJ/mol
Set up the equation and calculate:
q
P
= mc
H
2
O
T + nH
vap

= 3.14 kJ + 122 kJ = 125 kJ
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 50 of 50
Standard States and Standard Enthalpy
Changes
Define a particular state as a standard state.
Standard enthalpy of reaction, H

The enthalpy change of a reaction in which all
reactants and products are in their standard states.
Standard State
The pure element or compound at a pressure of 1
bar and at the temperature of interest.
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 51 of 50
Enthalpy Diagrams
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 52 of 50
7-7 Indirect Determination of H:
Hesss Law
H is an extensive property.
Enthalpy change is directly proportional to the amount of
substance in a system.

N
2
(g) + O
2
(g) 2 NO(g) H = +180.50 kJ
N
2
(g) + O
2
(g) NO(g) H = +90.25 kJ
H changes sign when a process is reversed
NO(g) N
2
(g) + O
2
(g) H = -90.25 kJ
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 53 of 50
Hesss Law
Hesss law of constant heat summation
If a process occurs in stages or steps (even hypothetically),
the enthalpy change for the overall process is the sum of
the enthalpy changes for the individual steps.
N
2
(g) + O
2
(g) NO
2
(g) H = +33.18 kJ
N
2
(g) + O
2
(g) NO(g) H = +90.25 kJ
NO(g) + O
2
(g) NO
2
(g) H = -57.07 kJ
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 54 of 50
Hesss Law Schematically
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 55 of 50
The enthalpy change that occurs in the
formation of one mole of a substance in the
standard state from the reference forms of
the elements in their standard states.

The standard enthalpy of formation of a
pure element in its reference state is 0.

H
f

7-8 Standard Enthalpies of Formation
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 56 of 50
Standard Enthalpies of Formation
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 57 of 50
Standard Enthalpies of Formation
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 58 of 50
Standard Enthalpies of Reaction
H
overall
= -2H
f

NaHCO
3
+ H
f

Na
2
CO
3


+

H
f

CO
2
+ H
f

H
2
O

Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 59 of 50
Enthalpy of Reaction
H
rxn
= H
f

products
- H
f

reactants
Prentice-Hall 2002 General Chemistry: Chapter 7 Slide 60 of 50
Table 7.3 Enthalpies of Formation of Ions
in Aqueous Solutions