Chapter

Seven
Thermodynamics: The First Law
CHEM 1211K
Fall 2013

Objec;ves
At the end of this chapter you will be able to:
Understand and calculate heat and work
Understand the principles behind expansion work
Explore the measurement of heat
Explore heat transfer at constant pressure and heat
capacity at constant pressure and constant volume
Understand the enthalpy of physical change and interpret
heaFng curves
Explore the relaFonship between enthalpy and internal
energy
Understand and use standard reacFon enthalpies and
enthalpies of formaFon.

Key Ideas
Heat and work are equivalent ways of
transferring energy between a system and its
surroundings.
The total energy of an isolated system is
constant.
The enthalpy change for a process is equal to
the heat released at constant pressure.

Why is it important?
The laws of thermodynamics govern chemistry
and life. They explain why reacFons take
place and let us predict how much heat
reacFons release and how much work they
can do.
Thermodynamics plays a role in every part of
our lives.
The energy released as heat can be used to
compare fuels, and the energy resources of food
are used to assess its nutriFonal value.
4

Introduc;on
Thermodynamics is the study of the
transformaFons of energy from one form into
another.
The rst law of thermodynamics
Keeps track of energy
How much energy a reaction produces or is needed
to occur

The second law of thermodynamics

Explains why some reactions take place why others
do not spontaneity of reactions
5

Introduc;on
Two fundamental concepts of
thermodynamics are heat (q) and work (w).
These are two forms of energy

Systems (7.1)
To keep track of changes in energy, we divide
the world into two parts:
System region of interest
Example: chemical reaction

-Surroundings everything
besides the system
Example: water bath
Note: in aqueous reactions, water is
part of the surroundings

System + surroundings = universe

Figure 7.3

Systems (7.1)
A system can be:
Open can exchange both matter
and energy with the surroundings
Example: human body

Closed Bixed amount of matter

but can exchange energy with the
surroundings
Example: hot or cold pack

Isolated no contact with its

surroundings; can exchange
neither matter nor heat
Example: liquid inside sealed thermally
insulated vacuum Blask

Figure 7.4

Systems (7.1)
SecFon summary:
In thermodynamics, the universe consists of a
system and its surroundings.
An open system can exchange both ma>er and
energy wit the surroundings.
A closed system can exchange only energy.
An isolated system can exchange nothing.
Unless speci*ied otherwise we will be working
from the perspective of the system
9

Work and Energy (7.2)

Work (w) is the process of achieving moFon
against an opposing force.
Work = opposing force x distance moved

w =F x d
force is measured in newtons (1 N = 1kgm/s2)
Force x distance = (1kgm/s2)(m)= kgm2/s2
1 kgm2/s2= 1 Joule; unit of energy
10

Work and Energy (7.2)

Energy is the capacity of a system to do work (at least,
thats one deniFon of it!).
A system that can do a lot of work possesses a lot of energy
A system can do work on its surroundings
When this occurs the capacity the system has to do work reduces;
energy is decreased;
w < 0, value of work is negative

The surroundings can do work on the system

When this occurs the capacity the system has to do work increases;
energy is increased
w > 0, value of work is positive

The total store of energy in a system is called its internal

energy (U).
U = q + w
11

Work and Energy (7.2)

Throughout thermodynamics:
X = Xnal - XiniFal
X represents difference in the property of X
If X has a negative value then the property decreased

U = Unal - UiniFal
From the perspective of the system:
U is positive, U> 0 then the internal energy increases
U is negative, U< 0 then the internal energy
decreases
12

Work and Energy (7.2)

U = q + w
If no other type of transfer of energy takes
place besides work, then:
q=0 and
U = w

13

Work and Energy (7.2)

SecFon summary:
Work is the transfer of energy to a system by a
process that is equivalent to raising or lowering a
weight.
For work done on a system, w>0 (w = +)
For work done by a system, w<0 (w = -)
The internal energy of a system may be changed
by doing work.
In the absence of other changes, U = w.
14

Expansion Work (7.3)

Two types of work:
Expansion work work arising from change in volume
of system
Figure 7.5
Simplest example is work done by or on a
system consisting of a gas in a cylinder.
w= F x d
F = Pressure x Area
w = Pressure x Area x d
w = -PexV (at constant external P)
The negative is present for sign convention
1L atm = 101.325 J
15

Expansion Work (7.3)

Two types of work:
Nonexpansion work work that does not involve a change
in volume of the system
Chemical reaction in a battery can do work by causing an
electrical current to Blow

16

Heat (7.4)
Remember: there are two terms that are used to
determine internal energy of a system
The internal energy of a system is the capacity of that
system to do work and the capacity for the system to
transfer heat

The internal energy of a system can also be changed

by transferring energy to or from the surroundings
as heat.
Heat energy transferred as a result of a
temperature difference
17

Heat (7.4)
Heat is energy in transiFon as a result of a
temperature dierence.
Heat and temperature are NOT the same thing!
This temperature dierence arises from the
energy of thermal moFon.
Molecules at higher temperature have a greater kinetic
energy than molecules at a lower temperature
Example: Two regions of molecules with different kinetic energies are
brought together
Region of molecules with greater kinetic energy bump into region
with less kinetic energy and transfer kinetic energy
Region that lost kinetic energy decreases in temperature
Region that gained kinetic energy increases in temperature
18

Heat (7.4)
Energy transferred as heat is denoted as q.
U = q + w

and

w = 0

If the internal energy of the system is changed by

transferring energy as heat (and no other
processes take place, such as work,) U = q.
w = 0, when there is no change in volume, at constant
pressure

When heat is lost from the system, q < 0, q is negaFve

When the system gains heat, q > 0, q is posiFve
19

Heat (7.4)
Like any form of energy, heat is oben
measured in Joules.
1 J = kgm2/s2

Other units of measurement:

calorie
1 calorie (cal) = 4.184 J

Calorie
1 Calorie (Cal) = 1000 calorie = 1 nutritional calorie

20

Heat (7.4)
Exothermic processes are those that release
heat into the surroundings.
Endothermic processes absorb heat from the
surroundings.

Figure 7.9

21

Heat (7.4)
SecFon summary:
Heat is the transfer of energy as a result of a
temperature dierence.
When energy is transferred as heat and no other
processes occur, U = q.
When energy enters a system as heat, q>0
(posiOve).
When energy leaves a system as heat, q<0
(negaOve).
22

The Measurement of Heat (7.5)

An inux of energy into a system typically
raises the temperature of the system.
To convert a temperature change into energy, we
need to know the heat capacity:
The amount of heat needed to cause a speciBic T in
a given amount of substance
ratio of heat supplied to T produced
heat supplied
Heat capacity =
temperature rise produced
q
C=
T

23

The Measurement of Heat (7.5)

If heat capacity is known, then the amount of heat supplied
can be calculated:

q = CT
Heat capacity is a extensive propertyit depends on the
amount of mafer present.
Specic heat capacity (speci*ic heat) Cs
amount of heat needed to raise the temperature 1.0 g of a
substance 1C
Units: J/gC

Molar heat capacity Cm

amount of heat needed to raise the temperature 1.0 mol of a
substance 1 degree
Units: J/molK

24

The Measurement of Heat (7.5)

The energy supplied as heat to a substance can
be calculated from mass, specic heat capacity,
and change in temperature.
q = mCsT
Looking at units:

q = (g)(J/gC)(C)= J

Similarly:

q = nCmT
Looking at units:

q = (mols)(J/molK)(K)= J
25

The Measurement of Heat (7.5)

Keep in mind that the soluGon of which the
temperature change is being measured is part of
the surroundings, and the system is closed.
Increase in soluFon temperature
Heat was released by the system to the surroundings.
The reacFon is exothermic.

Decrease in soluFon temperature

Heat was absorbed by the system from the
surroundings.
The reacFon is endothermic.
26

The Measurement of Heat (7.5)

Example: Calculate the nal temperature of a
200.0 g sample of stainless steel at 25.0oC aber
743 J of heat have been provided to the system.
Cs for stainless steel = 0.51 J/goC.
q = mCs T
Find T
Find Tinitial

T = Tfinal Tinitial

+743J = (200.0 g) (0.51J/gC)T

T = 7.284C

7.284C = Tfinal 25.00C

Tfinal = 32.3C
27

The Measurement of Heat (7.5)

Transfers of energy as heat are
measured with a calorimeter.

qcal = CcalT
Ccal is the heat capacity of the calorimeter
Each calorimeter is slightly different and
has a different ability to absorb heat
Calorimeters have to be calibrated
to determine the amount of heat each
absorbs
Figure 7.11

28

The Measurement of Heat (7.5)

When determining the changes in heat in a
system and the surroundings,
qsystem = -qsurroundings
And:

qsystem = -[qcal + qsurroundings ]

29

The Measurement of Heat (7.5)

Example: 100.0 grams of H2O(l) at 100C is mixed with
82.00 g of H2O(l) at 65.0 C. What is the nal
temperature of the mixture? The specic heat of H2O(l)
= 4.184 J/gC.
Find how hot and cool solutions are related qhot = qcold
Solve for Binal temp. of mixture Binal temp. is same for both H2O
-mhot Cs Thot = mcold Cs Tcold

-mhot Cs (Tf Tihot ) = mcold Cs (Tf Ticold )

-(100.0g)(4.184J/gC)(Tf 100C) = (82.00g)(4.184J / gC)(Tf 65.00C)
Tf = 84.2C
30

The Measurement of Heat (7.5)

Example: A small piece of calcium carbonate was placed
in a calorimeter with Ccal = 487.6 J/oC along with 100.0 mL
of hydrochloric acid. The temperature of the calorimeter
rose by 3.57oC. What is the value of U for this reacFon?
U = q + w , w = 0
U = q
q = -qcal

q = -CcalT
q = -[(487.6J / C)(3.57C)]
q = -1740 J

Check sign of q with increase or decrease of heat in system

Temperature increases, energy leaves the system in form of heat, negative q
31

The Measurement of Heat (7.5)

SecFon summary:
The heat capacity of an object is the raOo of the
heat supplied to the temperature rise produced.
Heat transfers are measured by using a calibrated
calorimeter.

32

The First Law (7.6)

In many processes, the internal energy
changes as a result of BOTH work and heat.

U = q + w

The transfer of energy as heat or work

on or by a system do not have to be
separate entities; they can occur at the
same time
Heat energy can be transferred to work
energy and vice versa

Figure 7.13

33

The First Law (7.6)

Example: A system was heated using 400.0 J
of heat, and its internal energy increased by
150.0 J. Calculate w. Was work done on the
system or by the system?
System gained heat
q, positive value

Internal energy increased

U, positive value

U = q + w
+150.0J = + 400.0J + w
250.0J = w

System performs work on the surroundings

Work is a negative value

34

The First Law (7.6)

The rst law of thermodynamics states that
the internal energy of an isolated system is
constant.

35

The First Law (7.6)

Internal energy is a state funcGon , a property
that depends only on the current state of the
system and is independent of how that state
was prepared.
Other state funcFons: P, V, T, and density

Work and heat (w and q) are NOT state

funcOons.
36

The First Law (7.6)

Figure 7.14

State function:
(a) take any path between two speciBic spots on the mountain, but
the difference in altitude between the two will always be equal
(independent of the path taken)
(b) The pathway between the two systems shown is different but
the difference in internal energy will be the same.
37

The First Law (7.6)

SecFon summary:
The rst law of thermodynamics states that the
internal energy of an isolated system is constant.
A state funcOon depends only on the current state
of a system.
The change in a state funcOon between two states
is independent of the path between them.
Internal energy is a state funcOon but work and
heat are not.
38

Heat Transfers at Constant Pressure (7.8)

Enthalpy, H is a state funcFon that allows us to
keep track of energy changes at constant
pressure.

H = U + PV

At constant pressure:

H = U+ PV

Still, U= q+ w and w = -PV:

H = q PV + PV
H = qp
39

Heat Transfers at Constant Pressure (7.8)

A change in the enthalpy of a system is equal
to the heat released or absorbed at constant
pressure.

H > 0 endothermic
H < 0 exothermic

40

Heat Transfers at Constant Pressure (7.8)

Example: In a given reacFon at constant pressure, 45 kJ of
energy leb the system as heat and 30. kJ of energy leb the
system as expansion work. What are the values of H and
U for this process? Is the reacFon endothermic or
exothermic?
Heat was removed from the system
H is a negative value

H = q p

H = -45 kJ, exothermic

System performs expansion work on the surroundings

Work is a negative value

U = q + w
U = -45kJ + (30. kJ )
U = 75 kJ

41

Heat Transfers at Constant Pressure (7.8)

SecFon summary:
The change in enthalpy of a system is equal to the
heat supplied to the system at constant pressure.
For an endothermic process, H > 0.
For an exothermic process, H < 0.

42

Heat Capaci;es at Constant Volume and

Constant Pressure (7.9)
Heat capaciFes depend on the condiFons under which
the heaFng takes place.
Molar heat capacity at constant volume:

q
Cm =
T

U = q + w

Work = 0 at constant volume, U = q

U
CV ,m =
T
Units of CV,m: J/molK
43

Heat Capaci;es at Constant Volume and

Constant Pressure (7.9)
Heat capaciFes depend on the condiFons under which
the heaFng takes place.
Molar heat capacity at constant pressure:
q
CP =
T
Work = 0 at constant pressure, H = q

H
CP,m =
T
Units of CP,m: J/molK

44

Heat Capaci;es at Constant Volume and

Constant Pressure (7.9)
CV,m and CP,m have very similar values for a given solid
or a specic liquid.
values are NOT very similar for gases
Example: CV,m and CP,m values are similar for H2O(l) but
not for H2O(g)

When heated, gases expand more than liquids

and solids
More energy is lost in the form of work when
heated at constant pressure
45

A Molecular Interlude: The Origin of the

Heat Capaci;es of Gases (7.10)
Atoms and molecules can store energy as
translaFonal, rotaFonal and vibraFonal energy.
Atoms

Linear
molecules

Non-linear
molecules

CV,m

(3/2)R

(5/2)R

3R

CP,m

(5/2)R

(7/2)R

4R

R = 8.314 J/molK
Example: Can use in q = mCV,mT type calculations.

46

Heat Capaci;es at Constant Volume and

Constant Pressure (7.9)
SecFon summary:
The molar heat capacity of an ideal gas at
constant pressure is greater than that at constant
volume.

47

The Enthalpy of Physical Change (7.11)

What actually happens when a solid melts?
When a liquid evaporates?
All phase changes have a heat Blow associated
with them.
Some are endothermic
Some are exothermic

48

The Enthalpy of Physical Change (7.11)

Phase changes that increase molecular contact are
Exothermic .
Examples: condensation, freezing, deposition
When a phase transiFon takes place at constant
pressure, the heat transfer accompanying the phase
change is equal to the change in enthalpy of the
substance.

qP = Hphase change
49

The Enthalpy of Physical Change (7.11)

Enthalpy of vaporizaGon, Hvap is the
dierence in molar enthalpy between the
vapor and the liquid states.
Hvap = Hm(vapor) Hm(liquid)
Hm molar enthalpy
All Hvap are positive
The stronger the intermolecular force present in a
molecule, the greater the Hvap.
50

The Enthalpy of Physical Change (7.11)

Example: How much energy, in kJ, is needed to
evaporate 50.0 g H2O if Hvap = + 40.7 kJ/mol?
When there is a phase change, there is not a T

q p = (H )(amount)
q p = (40.7kJ / mol)(n)

q p = (40.7kJ / mol)(2.77mol)

$
! 50.0g H 2O $!
1 mol
& = 2.77mol H 2O
#
&#
"
%" 18.02 g H 2O %

q p = 113 kJ

51

The Enthalpy of Physical Change (7.11)

Table 7.3

Hvap > Hfus for a given substance, this is related to the

strength of intermolecular forces present

52

The Enthalpy of Physical Change (7.11)

Enthalpy of fusion, Hfus is the enthalpy
change accompanying the melFng (fusion) of a
substance.
Hfus = Hm(liquid) Hm(solid)
Endothermic process

53

The Enthalpy of Physical Change (7.11)

Enthalpy of sublimaGon, Hsub is the molar
enthalpy change when a substance sublimes
(s g).

Hsub = Hm(vapor) Hm(solid)

Enthalpy, H is a state function

Value for enthalpy is the same if it
occurs in one step or multiple steps
Hsub = Hfus + Hvap

Figure 7.24

54

The Enthalpy of Physical Change (7.11)

VaporizaFon, fusion, and sublimaFon all have
reverse processes.
- VaporizaFon: liquid gas Endothermic process, Hvap (+)
- CondensaFon: gas liquid
- Fusion: solid liquid
- Freezing: liquid solid

Endothermic process, Hfus (+)

- SublimaFon: solid gas

- DeposiFon: gas solid

Endothermic process, Hsub (+)

55

The Enthalpy of Physical Change (7.11)

The enthalpy change for a reverse process has the same
value but the opposite sign of the enthalpy change for
the forward process (at the same temperature).

Hreverse process = - Hforward process

Vaporization (liquid gas) process is endothermic, Hvap (+)
Condensation (gas liquid) is the reverse process of
vaporization.
Hcon = - Hvap
Hcon is exothermic (-)
56

The Enthalpy of Physical Change (7.11)

SecFon summary:
The enthalpy change for a reverse reacOon is the
negaOve of the enthalpy change for the forward
reacOon.
Because it is a state funcOon, enthalpy changes
can be added to obtain the value for an overall
process.

57

Hea;ng Curves (7.12)

A heaGng curve is a graph showing the
variaFon in the temperature of a sample as it
is heated at constant rate and constant
pressure.

58

Hea;ng Curves (7.12)

H2O

Heating/
cooling

Endothermic
Phase Change
heating/cooling

Exothermic
Phase Change
heating/cooling

(J)

59

Figure 7.26

Hea;ng Curves (7.12)

H2O

Heating
/cooling

Endothermic
Phase Change

For phase changes: q = mol(H phase change )

heating/cooling

Phase Change
heating/cooling

For heating/cooling changes:

q = (mass)(Cs )(T ) or
q = (mol)(CP,m )(T )

Exothermic

(J)

60

Figure 7.26

Hea;ng Curves (7.12)

Example: How many joules of energy must be absorbed by 5.00 x 102 g of
H2O at 50.0oC to convert it to steam at 120oC? (Hvap for water = 40.7 kJ/
mol, CP,m (water) 75.3 J/mol oC, CP,m (steam) = 36.4 J/mol oC)
50C(liquid) 100C(liquid) 100C(vapor) 120C(vapor)
1) 50C(liquid) 100C(liquid)
q = (mols)(CP,m(water ) )(T )

! 5.00x10 2 g H 2O $! 1mol H 2O $
& = 27.75mol H 2O
#
&#
18.02g
H
O
"
%"
%
2

q = (27.75mol)(75.3J / molC)(100.0C 50.0C) = 104500J

2) 100C(liquid) 100C(vapor)
q = (mols)(H vap )

104500J +1129000J + 20200J = 1.25x10 6 J

q = (27.75mol)(40.7kJ / mol) = 1129kJ

3) 100C(vapor) 120C(vapor)
q = (mols)(CP,m(steam) )(T )
q = (27.75mol)(36.4J / molC)(120.0C 100.0C) = 20200J

61

Hea;ng Curves (7.12)

SecFon summary:
The temperature of a sample is constant at its
melOng and boiling points, even though heat is
being supplied.
The slope of a heaOng curve is steeper for a phase
with a low heat capacity than for one with a high
heat capacity.

62

Reac;on Enthalpies (7.13)

A thermochemial equaGon consists of a
chemical equaFon together with a statement
of the corresponding enthalpy change.
The enthalpy change for a reacFon is called the
enthalpy of reacGon, Hrxn.

C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ

Heat is a product then exothermic
Heat is a reactant then endothermic
63

Reac;on Enthalpies (7.13)

The stoichiometric coecients in thermochemical
equaFons must be interpreted as mols of reactants
and products.
Example below:
One mole of C6H12O6 reacts with six moles of O2 to
produce six moles of CO2 and six moles of H2O.

C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ

64

Reac;on Enthalpies (7.13)

Thermochemical reacFons should always be
interpreted as the enthalpy change for the reacFon
exactly as it is wriOen.
This specic amount of reacFon is one mole of
reacGon (mol rxn). This is where the units kJ/mol or J/
mol originate.

C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ

! 1mol rxn $ ! 3523kJ $
#
& or #
&
" 3523kJ % " 1mol rxn %
65

Reac;on Enthalpies (7.13)

The enthalpy change for a reverse reacFon has
the same value but an opposite sign as that of
the forward reacFon.

C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ

3523 kJ + 6 CO2 (g) + 6 H 2O(l) C6 H12O6 (l) + 6 O2 (g)
For the reverse reaction, change the sign of Hrxn.
66

Reac;on Enthalpies (7.13)

Example: What is the change in enthalpy when
425 g of C6H12O6 is burned in the presence of
excess oxygen gas?

C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ

Find moles of C6H12O6
Find moles of reaction
Find enthalpy change
! 425g C6 H12O6 $! 1mol C6 H12O6 $! 1mol rxn $! 3523kJ $
&#
&#
#
&#
& = 8310kJ
"
%" 180.18g C6 H12O6 %" 1mol C6 H12O6 %" 1mol rxn %
67

Reac;on Enthalpies (7.13)

SecFon summary:
A thermochemical equaOon is a statement of a
chemical equaOon and the corresponding reacOon
enthalpy, the enthalpy change for the
stoichiometric amounts of substances in the
chemical equaOon.

68

Standard Reac;on Enthalpies (7.15)

The enthalpy change for a reacFon depends on
the physical states of the products and reactants.
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + 802 kJ
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) + 890. kJ
Enthalpy of a reacFon depends on:
Phases of the reactants and products
CondiFons of reactants and products (example
pressure)
69

Standard Reac;on Enthalpies (7.15)

The standard state for a substance is its pure
form at exactly 1 bar of pressure.
Examples:
Sodium: Na(s)
Oxygen: O2(g)
Iron: Fe(s)

70

Standard Reac;on Enthalpies (7.15)

Enthalpy of reacFon also depends on the
condiFons at which the measurement was
taken.
Most texts and tables give data for reacFons in
which each product and reactant is in its standard
state.
Most thermochemical data are reported for 25oC
(298.15 K). Temperature is NOT part of the
deniGon of standard state. This is just the most
common temperature used in collecFng data.
71

Standard Reac;on Enthalpies (7.15)

The standard reacGon enthalpy (Ho) is the
reacFon enthalpy when reactants and
products are in their standard states.
Represented by Ho instead of H

72

Standard Reac;on Enthalpies (7.15)

SecFon summary:
Standard reacOon enthalpies refer to reacOons in
which the reactants and products are in their
standard state, the pure form at 1 bar.
They are usually reported for a temperature of
298.15 K.

73

Hesss Law (7.16)

Hesss law states that the overall reacFon
enthalpy is the sum of the reacFon enthalpies
of the steps into which the reacFon can be
divided.
Hrxn = Hrxn

Figure 7.30

74

Hesss Law (7.16)

Whatever you do to the rxn, do the same to
its H.
If you reverse a reacFon, change the sign on H.
If you have to mulFply the coecients in a
reacFon by a given integer, mulFply H by the
same integer.
When you add reacFons, add their H.
75

Hesss Law (7.16)

Example: Use the informaFon below to calculate
Ho for the reacFon:
4 FeO(s) + O 2(g) 2 Fe 2O 3(s)
2 Fe(s) + O 2(g) 2 FeO(s)
4 Fe(s) + 3 O 2(g) 2 Fe 2 O3(s)
4FeO(s) 4 Fe(s) + 2 O 2(g)
4 Fe(s) + 3 O 2(g) 2 Fe 2 O3(s)

H o = 544 kJ
H o = 1648 kJ
H o = 2(544 kJ) = +1088kJ
H o = 1648 kJ

4 FeO(s) + 4 Fe(s) + 3 O 2(g) 4 Fe(s) + 2 O 2(g) + 2 Fe 2 O3(s) H o = 560 kJ

4 FeO(s) + O 2(g) 2 Fe 2 O3(s)

H o = 560 kJ

76

Hesss Law (7.16)

SecFon summary:
According to Hesss law, thermochemical
equaOons for the individual steps of a reacOon
sequence may be combined to give the
thermochemical equaOon for the overall reacOon.

77

Standard Enthalpies of Forma;on (7.18)

The standard molar enthalpy of formaGon
(Hfo) of a substance is the enthalpy change
for the reacFon in which one mole of the
substance (in a specied state) is formed from
its elements in their most stable forms.
Only one mole of product can form
Fractional coefBicients for reactants can be used.

78

Standard Enthalpies of Forma;on (7.18)

Example: The standard molar enthalpy of formaFon for
phosphoric acid in the solid state is -1281 kJ/mol.
Phosphorous in its standard state is P4(s). Write the
equaFon that corresponds to the enthalpy of formaFon
for phosphoric acid.
Phosphoric acid - H3PO4(s)

H 2(g) + P4(s) + O 2(g) H 3PO 4(s) + 1281 kJ

Balance the reaction
3
1
H 2(g) + P4(s) + 2O 2(g) H 3PO 4(s) + 1281 kJ
2
4

79

Standard Enthalpies of Forma;on (7.18)

Standard enthalpies of formaFon can be used
to calculate enthalpies of reacFon.

o
rxn

= n H
n

o
f products

n H

o
f reactants

n = stoichiometric coefficients

80

Standard Enthalpies of Forma;on (7.18)

Example: Calculate the Ho298 for the following reacFon
from data below.
H f C3H8 = 103.8kJ / mol
H f H2O (l ) = 285.8kJ / mol

H f CO2 = 395.3kJ / mol

H f O2 = 0.0kJ / mol

C3 H 8 (g) + 5O2 (g) 3CO2 (g) + 4H 2O(l)

H rxn = [3mol(H f CO2 ) + 4mol(H f H2O ( l ) )][1mol(H f C3H8 ) + 5mol(H f O2 )]

H rxn = [3mol(395.3kJ / mol) + 4mol(285.8kJ / mol)]

[1mol(103.8kJ / mol) + 5mol(0.0kJ / mol)]
H rxn = [2329.1kJ][103.8kJ] = 2225.3kJ
81

Standard Enthalpies of Forma;on (7.18)

SecFon summary:
Standard enthalpies of formaOon can be combined
to obtain the standard enthalpy of any reacOon.

82

Bond Enthalpies (7.20)

In a chemical reacFon, bond breaking is
always endothermic and bond formaOon is
always exothermic.
The strength of a chemical bond is the bond
enthalpy (HB).

We can esFmate reacFon enthalpies if we

know the enthalpy changes that accompany
the breaking and making of bonds.
83

Bond Enthalpies (7.20)

Bond breaking is always endothermic.
Bond formaOon is always exothermic.
Bond energies can also be used to calculate
Horxn.

Horxn = HB reactants - HB products

Calculating Hrxn using bond energies: reactants products
Calculating Hrxn using Hf : products reactants
84

Bond Enthalpies (7.20)

Example: EsFmate the enthalpy of reacFon for the
combusFon of methane using the informaFon in Tables 7.7
and 7.8

Hrxn = [4(H B, C-H ) + 2(H B, O=O )][2(H B, C=O ) + 4(H B, H-O )]

Hrxn = [4(412kJ / mol) + 2(496kJ / mol)]
[2(743kJ / mol) + 4(463kJ / mol)]

Hrxn = [2640kJ / mol][3338kJ / mol)] = 698kJ / mol

85

Bond Enthalpies (7.20)

SecFon summary:
Bond enthalpies can be used to calculate
enthalpies of reacOon.
Bond breaking is endothermic.
Bond formaOon is exothermic.

86