GENERAL CHEMISTRY

P R ı N C ı P L E S A N D M O D E R N A P P L ı C AT ı O N S
ELEVENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Thermochemistry 7
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

Slide 7 - 1 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 CONTENTS
Thermochemistry 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 Application of the First Law to
Chemical and Physical Changes
7-7 Indirect Determination
of DrH: Hess’s Law
7-8 Standard Enthalpies of
Formation
7-10 Spontaneous and Nonspontaneous
Processes: An Introduction

Slide 7 - 2 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 7-1 Getting Started: Some Terminology
Thermochemistry is the branch of chemistry concerned with
the heat effects that accompany chemical reactions.
Let us think of the universe as being comprised of a system
and its surroundings.
A system is the part of the universe chosen for study.
The surroundings are that part of the universe outside the
system with which the system interacts.
An open system freely exchanges energy and matter with its
surroundings.
A closed system can exchange energy, but not matter, with its
surroundings.
An isolated system does not interact with its surroundings.

Slide 7 - 3 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 FIGURE 7-1
Systems and their surroundings

Slide 7 - 4 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Energy is the capacity to do work.
Work is done when a force acts through a distance. Moving
objects do work when they slow down or are stopped.
The energy of a moving object is called kinetic energy.
Potential energy is energy resulting from condition, position,
or composition; it is an energy associated with forces of
attraction or repulsion between objects.
The kinetic energy associated with random molecular motion
is called thermal energy.

Slide 7 - 5 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 1 J = 1 kg m2 s–2

Kinetic Energy
2
1 m
Ek = mu2 [Ek ] = kg = J
2 s
Work = Force x distance

w=Fxd
m m
= mxaxd [w ] = kg 2 = J
s
Slide 7 - 6 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.
 7-2 Heat
Heat is energy transferred between a system and its
surroundings as a result of a temperature difference.
Energy that passes from a warmer body (with a higher
temperature) to a colder body (with a lower temperature) is
transferred as heat.
At the molecular level, molecules of the warmer body, through
collisions, lose kinetic energy to those of the colder body.
Thermal energy is transferred heat flows until the average
molecular kinetic energies of the two bodies become the
same, until the temperatures become equal.
Heat, like work, describes energy in transit between a system
and its surroundings.

Slide 7 - 7 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 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

Slide 7 - 8 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Heat Capacity
The quantity of heat required to change the temperature of a
system by one degree.
If system is one mole of substance Molar heat capacity, cp,m
If system is one gram of substance Specific heat capacity, cp

When the temperature of a system increases (Tf > Ti), ΔT is positive.

A positive q signifies that heat is absorbed or gained by the system.

When the temperature of a system decreases (Tf < Ti), ΔT is

negative. A negative q signifies that heat is evolved or lost by the
system.
Slide 7 - 9 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.
1A. How much heat, in kilojoules (kJ), is required to raise the
temperature of 237 g of cold water from 4.0 to 37.0 °C (body
temperature)? (Assume the specific heat of water is 4.18 J g-1 °C-1
throughout this temperature range.)

Q = m.Cp. ∆T

Slide 7 - 10 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 Law of conservation of energy
In interactions between a system and its surroundings the
total energy remains constant— energy is neither created
nor destroyed.

qsystem + qsurroundings = 0

qsystem = –qsurroundings

Slide 7 - 11 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 Experimental Determination
of Specific Heat Capacities

FIGURE 7-3
Determining the specific heat of lead – Example 7-2 illustrated

Slide 7 - 12 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

2A. When 1.00 kg lead (specific heat = 0.13 J g -1 °C-1) at 100°C
is added to a quantity of water at 28.5 °C, the final temperature of
the lead water mixture is 35.2 °C. What is the mass of water
present?

Slide 7 - 13 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 7-3 Heats of Reaction and Calorimetry
Heat of reaction, qrxn.
The quantity of heat exchanged between a system and its surroundings when
a chemical reaction occurs within the system, at constant temperature.
An exothermic reaction is one that produces a temperature increase in an
isolated system or, in a nonisolated system, gives off heat to the surroundings.
For an exothermic reaction, the heat of reaction is a negative quantity
(qrxn < 0).
In an endothermic reaction, the corresponding situation is a temperature
decrease in an isolated system or a gain of heat from the surroundings by a
nonisolated system. In this case, the heat of reaction is a positive quantity
(qrxn > 0).
Heats of reaction are experimentally determined in a calorimeter, a device for
measuring quantities of heat.

Slide 7 - 14 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 A bomb calorimeter assembly

qrxn = –qcal

qcal = q bomb + q water + q wires +…

Define the heat capacity of the

calorimeter:
qcal = ∑mici∆T = Ccal∆T
all i

FIGURE 7-5
A bomb calorimeter assembly

Slide 7 - 15 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

3A. Vanillin is a natural constituent of vanilla. It is also
manufactured for use in artificial vanilla flavoring. The combustion
of 1.013 g of vanillin, C8H8O3, in the bomb calorimeter causes the
temperature to rise from 24.89 to 30.09 °C. What is the heat of
combustion of vanillin, expressed in kilojoules per mole?

Slide 7 - 16 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 7-4 Work
Work involved in the expansion or compression of gases is called
pressure-volume work.
W= - P. ∆V (in Joule)

5A. How much work, in joules, is involved when 0.225 mol N2 at a

constant temperature of 23 °C is allowed to expand by 1.50 L in
volume against an external pressure of 0.750 atm?

General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 17
 7-5 The First Law of Thermodynamics

A system contains only internal energy (U).

A system does not contain heat or work.
These only occur during a change in the system.

∆U = q + w

An isolated system is unable to exchange either heat or

work with its surroundings, so that DUisolated system = 0

Slide 7 - 18 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Any energy entering the system carries a positive sign. Thus,
if heat is absorbed by the system, q > 0. If work is done on
the system, w > 0.
Any energy leaving the system carries a negative sign. Thus, if
heat is given off by the system, q < 0. If work is done by the
system, w < 0.
In general, the internal energy of a system changes as a result
of energy entering or leaving the system as heat and/or
work.
If, on balance, more energy enters the system than leaves, ΔU
is positive. If more energy leaves than enters, ΔU is
negative.
A consequence of ΔUisolated system = 0 is that ΔUsystem= -
ΔUsurroundings; that is, energy is conserved.

Slide 7 - 19 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 FIGURE 7-10
Illustration of sign conventions used in thermodynamics

Slide 7 - 20 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

6A. In compressing a gas, 355 J of work is done on the
system. At the same time, 185 J of heat escapes from the
system. What is ΔU for the system?

∆U = Q + W
∆U = (+355 J) + (-185 J )
∆U = 170 J

Slide 7 - 21 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 7-6 Application of the First Law to
Chemical and Physical Changes
Reactants → Products
Ui Uf

∆U = Uf −Ui

∆U = qrxn + w

In a system at constant volume (bomb calorimeter):

∆U = qrxn + 0 = qrxn = qv

But we live in a constant pressure world!

How does qp relate to qv?

Slide 7 - 22 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Chemical reactions are not ordinarily carried out in bomb
calorimeters. The metabolism of sucrose occurs under the
conditions present in the human body.
The combustion of methane (natural gas) in a water heater
occurs in an open flame.
The usual other way is in beakers, flasks, and other
containers open to the atmosphere and under the constant
pressure of the atmosphere.
In many reactions carried out at constant pressure, a small
amount of pressure volume work is done as the system
expands or contracts.
7-6 Application of the First Law
Enthalpy, H, is the sum of the internal energy and the
pressure volume product of a system:

H = U + PV
The enthalpy change, ΔH for a process between initial and final
states is
∆H = Hf – Hi = qP
For a constant pressure process, the heat transferred is equal to
the enthalpy change, ΔH, of the system.

So; ΔU = q+w

∆U = ∆H– P∆V
Slide 7 - 24 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.
Enthalpy of Reaction: DH

2 CO (g) + O2 (g) 2 CO2 (g) ΔH = –566 kJ mol–1

per mole of reaction

one mole of reaction refers to the situation in

which the extent of reaction is equal to 1 mol

C12H22O11 (g) + 12 O2 (g) 12 CO2 (g) + 11 H2O (g)

ΔH = –5.65✕103 kJ mol–1

Slide 7 - 25 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

7A. What mass of sucrose must be burned to produce 1.00 ×
103 kJ of heat? (Molar mass of sucrose is 342.30 g/mol, enthaply
of reaction is –5.65✕103 kJ mol–1 )

Heat is given off, so has a negative sign.

Enthalpy Change Accompanying a Change in State of Matter
The heat required to vaporize a fixed quantity of liquid is called
the enthalpy (or heat) of vaporization. liquid chosen if one mole,
we can call this quantity as molar enthalpy of vaporization.

Molar enthalpy of vaporization:

H2O (l) → H2O(g) ∆H = 44.0 kJ at 298.15 K

The energy requirement for melting of a solid is called the

enthalpy (or heat) of fusion. For the melting of one mole of
ice:
Molar enthalpy of fusion:
H2O (s) → H2O(l) ∆H = 6.01 kJ at 273.15 K

Slide 7 - 27 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

8A. What is the enthalpy change when a cube of ice 2.00 cm on
edge is brought from -10.0 C to a final temperature of 23.2 C? For
ice, use a density of 0.917 g/cm3, a specific heat of 2.01 J g-1 C-1
and an enthalpy of fusion of 6.01 kJ/mol.
 Standard States and Standard
Enthalpy Changes
Standard enthalpy of reaction, ∆Hº
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.

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 7-7 Indirect Determination of ∆H:
Hess’s Law
• ∆H is an extensive property.
Enthalpy change is directly proportional to the amount of
substance in a system.

N2(g) + O2(g) → 2 NO(g) ∆H° = +180.50 kJ mol–1

½N2(g) + ½O2(g) → NO(g) ∆H° = +90.25 kJ mol–1

• ∆H changes sign when a process is reversed

NO(g) → ½N2(g) + ½O2(g) ∆H° = −90.25 kJ mol–1

Slide 7 - 30 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

 • Hess’s law of constant heat summation

½N2(g) + O2(g) → NO(g) + ½ O2 (g) ∆Hº = +90.25 kJ mol–1

NO(g) + ½O2(g) → NO2(g) ∆Hº = –57.07 kJ mol–1

½N2(g) + O2(g) → NO2(g) ∆Hº = +33.18 kJ mol–1

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

Slide 7 - 31 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

9B. From the data, determine the standard enthalpy of combustion
of one mole of 2-propanol, CH3CH(OH)CH3(l).
 7-8 Standard Enthalpies of Formation, ∆Hfº
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 is 0 for a pure element in its reference form.

Listed here are the most stable forms of several elements at 298.15
K, the temperature at which thermochemical data are commonly
tabulated.
Na(s) H2(g) N2(g)
O2(g) C(graphite) Br2(l)

Slide 7 - 33 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 7 - 34 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.
 Standard Enthalpies of Reaction

∆Hº = ∑np∆Hfº (products) −∑nr∆Hfº (reactants)

Slide 7 - 35 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

11A. Use data from Table 7.2 to calculate the standard enthalpy
of combustion of ethanol, CH3CH2OH(l), at 298.15 K.

CH3CH2OH(l) + 3O2 (g) → 2 CO2 (g) + 3 H2O (g)

 Sample Questions

Slide 7 - 37 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

4A. Two solutions, 100.0 mL of 1.00 M AgNO3(aq) and 100.0 mL
1.00 M NaCl(aq), both initially at 22.4 °C, are added to a isolated
Styrofoam-cup calorimeter and allowed to react. The temperature
rises to 30.2 °C. Determine qrxn per mole of AgCl(s) in the
reaction.
Ag+(aq) + Cl-(aq) → AgCl(s)

qrxn = –qcal

Slide 7 - 38 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

12A. The overall reaction that occurs in photosynthesis in plants
is
6 CO2(g) + 6 H2O(l) → C6H12O6(s) + 6 O2(g) ΔH° = 2803 kJ
Determine the standard enthalpy of formation of glucose,
C6H12O6(s), at 298 K.
When heat is absorbed by ice (the system)
it melts. The quantity q for the system is

1. positive. Catch: Photo of Ice

page 498
2. negative.
3. 0

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 The figure below shows the heating curve for water. It traces the changes in
temperature as ice, initially at -20 oC, is gradually heated to produce liquid
water at +20 oC. When the ice (the system) melts,

1. Temperature remains constant,

therefore no heat is being added to
or removed from the system during
the melting of the ice.

2. Although T is constant, heat is

added to convert H2O(s) to H2O(l)

3. Although T is constant, heat is

removed to to convert H2O(s) to
H2O(l)

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Determine DH and DU for the reaction and conditions depicted below.
Note: 1 Pa = 1 N m-2.

V1= 0.120 m3 V2= 0.110 m3

DH DU
1. 250 kJ, 251 kJ

2. 250 kJ, 249 kJ

3. -250 kJ, -251 kJ

1x105 Pa
4. -250 kJ, -249 kJ qP = 250 kJ
5. -250 kJ, -250 kJ
T=300 K

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 Ice (the system) melting is
Catch: Photo of Ice
page 498
1. an exothermic process.

2. an endothermic process.

3. neither exothermic nor endothermic

since the temperature of the system
remains constant (0 oC at 1 atm).

Note: a bit tricky perhaps until chapter 13.

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