Main references

Chemical Thermodynamics

Most of the text and pictures for these slides

were based or taken from the following
books:

Chem 17 Lecture 1

Petrucci, General Chemistry, 10th ed., 2010

Whitten, General Chemistry, 8th and 9th ed, 2010

The rest were taken from various Internet

sources.
2

Chapter Goals (Part 1)

o
o
o
o
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Chapter Goals

Heat Changes and Thermochemistry

The First Law of Thermodynamics
Basic Thermodynamic Terms
Enthalpy Changes
Thermochemical Equations/Hesss Law
Standard States and Standard Enthalpy
Changes
Standard Molar Enthalpies of Formation,
Hfo

o Estimation of H based on Bond

Energies
o Changes in Internal Energy, E
o Relationship of H and E

Energy is in the core of our lives.

Energy: cant live without it.

It is the very essence of our existence.

Body/Physiology: Food/ Exercise

Energy source/storage
Gadgets/devices/machines.
Transportation Manufacturing
industries
Dependence in oil,
Environmental impact:
Global warming
Pollution

Cost of goods/services.
5

Thermodynamics

Core of Energy = Core of Science

The study of changes in

energy and transfers of
energy (interconversions of
energy).

Thermochemistry: is that special branch dealing

with studies of energy changes accompanying
chemical reactions and physical processes.

We will address 3 fundamental questions.

o Will two (or more) substances react
when they are mixed under specified
conditions?
o If they do react, what energy changes
and transfers are associated with their
reaction?
o If a reaction occurs, to what extent does
it occur?

1st Law of Thermodynamics

Energy is neither created nor destroyed in
reactions and physical changes.

Recall the different forms of

energy

It is just transferred from one form to

another.

The combined
amount of
energy in the
universe is
constant.

10

ENERGY

ENERGY : E
The capacity to do work or to
transfer heat.

In the atomic/molecular level:

Potential energy of the electrons (=
electrostatic force between e-/nucleus and
the surrounding atoms;
Kinetic Energy of the electrons (electrons are
constantly moving, KE
0 as T= 0 K.

Kinetic Energy, eK energy of motion.

Potential Energy, V energy possessed by
virtue of its position or composition. Stored
energy.
Associated with forces of attraction or repulsion
between objects.

Other forms
Electrical, thermal, nuclear, chemical.

11

12

Total Energy, E versus

Internal Energy, U

Is there a zero-energy system?

Suppose T
0 K.

Total Energy of a system is the sum of all the

energy (macroscopic) and (nano/atomic level)

K.E.
0 , howeverCC

approaches

We can differentiate between

energy in the macro level and the
atomic level.

We are most often interested in the Total

Energy Change, E.
E = KE + PE+ U + other forms.

However, chemists normally work mostly with systems whose changes

only involved internal energy, U
14

13

Total Energy, E versus

Internal Energy, U

Internal energy, U and U

 E = KE + PE+ U + other forms

 U: Internal Energy: mostly in the form of a stored
chemical energy
Food/fuelderived from P.E. stored in atoms
(arrangement of molecules).
The chemical energy is released when these molecules
undergo chemical changes
Combustion, metabolism (think of ATP/biomolecules).

 You will learn in your higher chemistry

courses that the Internal energy, U is the sum
of different energies.
In the molecular level:
U = Urotational + Uvibrational + Utranslational + Uelectronic + Uothers.
The energy related to motion (rot, vib, trans) are the
biggest contributing energy factor to physical
changes while the Uelectronic as expected contributes
to the chemical changes.

15

Thermodynamic Systems
o Chemical systems tend toward a state of
maximum disorder.
Common examples:
A mirror shatters when dropped and
does not reform.
It is easy to scramble an egg and
difficult to unscramble it.
Food dye when dropped into water
disperses.
17

16

Two basic ideas of importance for

thermodynamic systems.
1. Chemical systems tend toward a state of
minimum potential energy.
H2O flows downhill.
Objects fall when dropped.
The energy change: E
Epotential = mgh
Epotential = mg(h)
18

Some Thermodynamic Terms

First Law of Thermodynamics

The substances involved in the

chemical and physical changes
under investigation are
collectively called the system.

Can be summarized for the system as:

Internal energy of the system = heat + work
U = q + w (in mathematical form)

The environment around the

system is called the
surroundings.

The internal energy is changed by the flow

(in/out) of heat, q or work, w or both.

The system plus the surroundings

is called the universe.
19

20

Open/Closed/Isolated System
How does the system
interact with the
surroundings?

Open : energy and matter can be

transferred to/from the surroundings.
Closed: energy can be transferred.

OPEN, CLOSED, ISOLATED

Systems

Isolated: neither energy nor matter can be

transferred. Therefore, system does NOT
interact with the surroundings anymore.
21

Is the system open or closed?

Reactions in a beaker
or a crucible?

22

Putting constraints to the

system of study.

Heating of a
substance inside
a tightly-sealed
container (e.g pressure
cooker?)

What separates the system to

the surroundings ?
Boundary or Walls

1. Rigid Wall (Non-movable) vs.Nonrigid (Movable)

2. Adiabatic vs. Thermally-Conducting
23

24

Test yourself
How would you describe the
state of the system?

Identify if the system is open, closed,

isolated:
A. Frozen river
B. Water and ethanol solution inside a
thermos.
C. Brine (salt) solution inside a tightly sealed
glass container.

Naming the different thermodynamic

properties of the system.
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25

Thermodynamic State

1st Law: U= q + w

The set of conditions that specify all of the

properties of the system is called the
thermodynamic state of a system.

Surroundings
System

work

T, P, V, n,

State 1

The state include:

The number of moles and identity of each
substance. (n)
The physical states of each substance (s, l, g)
The temperature of the system (T).
The pressure of the system (P).

State 2

27

Thermodynamic Terms:
State Function

Process
Chemical reaction or
Physical transformation
* U since
we are
interested with
System
changes in U 28

Change

Thermodynamic Terms:
State versus Path Function

The properties of a system that depend only on

the state of the system are called state functions.
State functions are always written using capital letters.

An analog to a state function is the energy

required to climb a mountain taking two different
paths.
E1 = energy at the bottom of the mountain
E1 = mgh1

The value of a state function is independent of

pathway and NOT in which the system came to be
in that state.

E2 = energy at the top of the mountain

E2 = mgh2

Therefore
E = E2-E1 = mgh2 mgh1 = mg(h)

Otherwise: a property is a path function (pathdependent function).

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30

Myth of Sisyphus and the

Analogy for Work (path function)

Some Thermodynamic Terms

Notice that the energy change in
moving from the top to the bottom is
independent of pathway but the work
required may not be!
Some examples of state functions are:

Sisyphus was condemned by the

Greek Gods for eternity to carry a
boulder of rock to the top of the hill,
which he rolls down back once he
reaches the top.

T, P, V, E, U, H, G and S

Examples of path (non-state

functions) are:

One must imagine Sisyphus happy. "The

struggle itself towards the heights is enough to
fill a man's heart."

A. Camus on the absurdity of

life. Finding meaning in a
Sisyphean task.

q, w

Intensive vs. Extensive Property

Thermodynamic properties could be either:
Extensive: dependent on the amount of
substance. The larger the amount of
substance, the larger the value of the property.
e.g. Energy, volume, heat content,
number of moles (n)
Intensive: amount-of-substance independent.
P, Temperature (T), density, U/n, V/n
33

I could not emphasize more that were

interested in measuring changes
Thermodynamics
changes in functions.
We can define the change of any function X as:

Process: X = Xfinal Xinitial

Reactions: Y = Yproducts Yreactants
If X increases, X > 0 (positive)
If X decreases, X < 0. (negative)
34

Heat: associated with the process of

thermal energy transfer

Heat, work, heat capacity,

specific heat

Thermal Energy: Kinetic energy associated with

random molecular motion. In general, heat is
proportional to temperature.

+ Some more other

concepts

Energy is transferred between a system

and its surroundings as a result of a
temperature difference (heat transfer)
and work (done by or done to the
system).
<U = q + w>
35

Heat flows from hotter to colder region.

Results:
Temperature may change.
Phase may change (an isothermal process).

36

Endothermic versus Exothermic

Process/Reactions

Units for Heat:

Calorie (cal)

Exothermic reactions release energy in the form

of heat.

The quantity of heat required to change the

temperature of one gram of water by one
degree Celsius.

Example: Combustion reactions and reactions of

formation.

Joule (J)

Propane

SI unit for heat is J. Often we used kJ

(kilojoules in calculations).

Butane

C 3H 8 (g) + 5 O 2(g) 3 CO 2(g) + 4H 2 O ( l ) + 2.22 103 kJ

2 C 4 H10(g) + 13 O 2(g) 8 CO 2(g) + 10 H 2O ( l ) + 5.78 103 kJ

1 cal = 4.184 J

Physical process: Fusion, Cooling, Condensation

37

Constants: used in energy

calculations

Endothermic Processes
Endothermic Reaction/processes
Requires the absorption of energy from
surroundings.

Examples:
Chemical bond dissociations.
Melting, heating, vaporization, sublimation.

aA+ bB+ q cC + dD
aA + bB cC + dD

38

H = + value
39

As mentioned, joules = J; kilojoules = kJ.

calories = cal = 4.184 J
Gas constants:
R = 8.3145 J mol-1K-1
R = 0.08206 L atm mol-1 K-1
R = 0.081345 L bar mol-1 K-1
Temperature: Kelvin scale: K = C + 273.15
Pressure: 1 atm = 760 torr = 760 mm Hg
1 bar, 1 Pascal (SI units) 40

Concept of Pressure

Try this.

Pressure = Force per unit area, P = F/A

in N m-2
Work = -PV; thus, P = |-Work| / |V |
Conversion from Torr to atm.
The atmospheric (external barometeric)
pressure on a mountain was found to be
750 Torr;
What is the pressure in
atm?
milliTorr?

cm-Hg?
Bar ?

If a system is compressed by 50.0 L-atm;

calculate the equivalent work value in kJ.

A 1.00 mole of an ideal gas at 200C is

confined in a 10.0 liter of container.
Calculate the pressure of the gas.
in atm.
in Torr.
(Hint: Use the ideal gas law).

41

42

Enthalpy Change:

Energy Units (SUMMARY)

Most common
chemical and physical changes occur at
constant Pressure.

For Chem 17 purpose:

1 J (joule) = 1 N m = 1 kg m-2 s-2.
1 cal = 4.184 J (exact)
1 kPa L = 1 J (joule)
1 bar L = 100 J
1 atm L = 101. 325 J (exact)
Note 1.0 atm = 101.325 kPa = 1.01325 bar = 760 Torr

Chemistry in the lab is frequently done in

open beakers on a desk top at atmospheric
pressure.
Because atmospheric pressure only changes
by small increments, this is almost at constant
pressure.

Practice: Calculate the Work involved for the isothermal

expansion of a 1.0 mol of an ideal gas with Vinitial = 5.00 L
to a final state Vfinal = 10.0 L, P is held constantly at 1kPa.
Express your answer in kcal and kJ.

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43

H, Heat Change, Heat of

Reaction

H = Enthalpy*

H = Heat Change = Heat of Reaction = Hrxn

Hrxn = Hproducts - Hreactants

Hrxn tells us if the reaction produces or consumes

heat.

H = change in enthalpy,

If Hrxn < 0 the reaction is exothermic.

If Hrxn > 0 the reaction is endothermic.

H = Hfinal Hinitial = qp
Hreaction = Hproducts Hreactants

* Also often called Heat content
this term is not recommended to be

used anymore
45

Exothermic reactions generate specific

amounts of heat.

Absolute enthalpy (heat content) of a system if impossible/if not difficult

to know;so were interested in the change in enthalpy.

Changes in processes ---we can measure!

46

Thermochemical Equation
Balanced chemical reaction plus the H value for the
reaction.

The potential
energies of the
products are
lower than the
potential energies
of the reactants.
Earequired to
get the reaction
started
CH4/O2--spark

For example, this is a thermochemical equation.

C5 H12( l ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( l ) + 3523 kJ

1 mole

8 moles

5 moles 6 moles

The stoichiometric coefficients in

thermochemical equations must be
interpreted as numbers of moles.
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48

Thermochemical Equation

Thermochemical Equation

C 5 H12( l ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( l ) + 3523 kJ

C 5 H12( l ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( l ) + 3523 kJ

1 mole

1 mole

8 moles

5 moles 6 moles

3523 kJ/ mol-rxn

3523 kJ/ 1 mol C5H12
3523 kJ/ 8 mol O2
3523 kJ/ 5 mol CO2
3523 kJ/ 6 mol H2O
49

8 moles

5 moles 6 moles

3523 kJ/ mol-rxn

How much heat is released for the
combustion of 1.0 g of pentane?
Versus
H=? evolved for burning 100.0 g of
pentane?

50

Thermochemical Equation

Thermochemical Equation

C 5 H12( l ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( l ) + 3523 kJ

C 5 H12( l ) + 8 O 2(g) 5 CO 2(g) + 6 H 2 O ( l ) + 3523 kJ

1 mole

1 mole

8 moles

5 moles 6 moles

- 3523 kJ/ mol-rxn

8 moles

5 moles 6 moles

- 3523 kJ/ mol-rxn

How many ____ of water is formed

from the burning of 120 g of pentane?
(a) moles (b) grams (c) liters

How many kJ of heat is released if

440 g of CO2 is produced?
51

Guidelines in using thermochemical

equations and enthalpy diagrams.

52

Guidelines in using thermochemical

equations and enthalpy diagrams.
Enthalpy, H is an extensive property, but if we
use or Hm we refer to a molar enthalpy (in kJ/mol)

Enthalpy is an extensive property:

The magnitude of the H is directly proportional to the
amount of the the reactant consumed in the process.

CH4 + 2O2  CO2 + H20

H = - 890 kJ

For 1 mole CH4 produces(releases) 890 kJ, therefore, if

your have 3 moles of CH4 (instead of 1 mole):
Hrxn = amount of heat released =
3 mol of CH4 * 890 kJ/mol = -2670 kJ
53

Hm = q/n
Heat, q = n Hm
* qp: for reactions done at constant P.

54

Practice Exercise:

Practice Exercise:

How much heat is evolved when 0.50 mol of

Na(s) reacts with excess water?
Na(s) + H2O (l) 1/2 H2 (g) + NaOH(aq) + 184 kJ

What is qrxn for the reaction of 0.75g of Na(s)

with excess H2O?

Na = 23.0 g/mol

You do it!

How much heat is evolved when 0.50 mol of

Na(s) <<MW 23.0>> reacts with excess
water?
Na(s) + H2O (l)

 1/2 H2 (g) + NaOH(aq) + 184 kJ

Na(s)+H2O (l)  H2(g)+NaOH(aq) H = - 184kJ

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56

More guidelines
qrxn (1) = (0.50 mol Na)(-184 kJ/1 mol Na)
= -92 kJ
92.0 kJ of heat was evolved/
released to surroundings.

2. The Hrxn is equal in magnitude but opposite in

sign to the H for the reverse reaction.

2H2O(l) +O2 (g) 

H2O2(l) H= + 196 kJ

H2O2 (l)  2H2O (l) +O2 (g) H= - 196 kJ

qrxn(2) =(0.75g Na) (1/23g
184kJ/mol)
= - 6.0 kJ

mol-1)(-

What is the H if 1 mol of H2O is produced instead?

Answer:
57

s
More
guidelines

CH4(g) +O2 (g)  H2O(l) +CO2 (g) H= -802 kJ

IS the new H

Less heat is available for transfer to surroundings

because H2O(g) has greater heat content than
H2O(l).
Conversion of H2O(l)  H2O(g) is endothermic,
that requires heat absorption of +88kJ.

H2O(g) + CO2 (g) H= -? kJ

(= > or < )

58

Answer: H = -714 kJ

The Hrxn depends on the state of the reactants and products.

CH4(g) +O2 (g) 

(-196 kJ/ 2 mol H2O) * 1 mol = - 98.0 kJ

Therefore, it is important to specify the states of the

reactants and products in the thermochemical
equation.

- 802 kJ
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60

Temperature Changes
Heat measurements

CALORIMETRY
The science of
measurement of heat

Recall what T and q (heat) mean.

They are not the same.
T = proportional to the ave. kinetic energy
of the particles

Monitoring changes in
temperature before and
after a process.

The higher the KE, the higher the T.

If T is increased, the velocities of the particles
is increased.

61

Temperature Changes and

Heat measurements
Recall that heat is energy (thermal energy)
that is transferred between objects
caused by differences in their temperature.

62

Heat (exchanged between

surroundings and system) is
proportional to the the T

Heat, q = C T

Heat is passed spontaneously from the

warm region to the cold region.
The energy transfer can be seen as
collision between the cold particles and
the hot particles.
63

How do we measure enthalpy

changes for processes?

By the 1st law: qsurroundings + qsystem = 0

Thus, qsystem = - qsurroundings
64

Coffee-cup calorimeters

Calorimetry -- determination of changes in energy

with a chemical or physical processes.
We measure T-changes (T) when a system
absorbs or releases energy
Calorimeters = tools used for calorimetry
Many types:
DSC, bomb-calorimeters and
simple calorimeters which can be used to measure
T-changes of a known substance (e.g. H2O), with
known specific heat.
Example: Coffee cup calorimeter
65

A coffee-cup
calorimeter is used to
measure the amount
of heat produced (or
absorbed) in a
reaction at constant P
This is one method to
measure qP for
reactions in solution.
A simple calorimeter.
Well insulated and therefore isolated.
Measure temperature change.
qrxn = -qcal

66

Coffee-cup calorimeter can be used to

measure heat changes involved in
reactions.

Warning!

If an exothermic reaction is performed in a

calorimeter, the heat evolved by the reaction is
determined from the temperature rise of the
solution..
surroundings

qrxn = -(qcal + q aq. solution)

Amount of heat gained by calorimeter is called the heat
capacity of the calorimeter or calorimeter constant.

Dont be confused with the qcal term. In the

lab your surroundings is composed of
both the aqueous solution and the styroball. You equated then the qsurroundings to
the qcal (which is qstyro + qH2O).
In many problems in gen-chem books, the
value of the solution will be mentioned so
you must calculate the total qcal .

The value of the calorimeter constant is determined by adding a

specific amount of heat to calorimeter and measuring the
temperature rise.
67

68

Simple Calorimetry: Other

Applications

Energy units // Other terms

1 Joule = 1 kg m2 s-2
1 cal = 4.184 J

Measurement of specific heat of materials

Adiabatic: no heat transferred allowed.

(e.g. a stoppered bottle (thermos/Dewar
flask).

69

Measurement of Heat capacity

(and specific heat)

70

Calorimetery Problem
(high school method)

The quantity of heat required to change the

temperature of a system by one degree.
Molar heat capacity, C
System is one mole of substance.

If we consider only the heat transfer

between the solution and the system,
without considering the calorimeter itself
(e.g. styrofoam cup)

Specific heat capacity, c or s.

System is one gram of substance

Heat capacity
(Mass of system) x specific heat.

The main assumption here: the calorimeter is non-interacting

(does not absorb or conduct heat).
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72

Practice Exercise
heat capacity measurement

Specific Heat/Heat capacity

Measurements
(a) A 150.0 g sample of lead is heated to the temperature of boiling
water (100.C).
(b) A 50.0 g sample of water is added to a thermally insulated
beaker, and its temperature is found to be 22C.
(c) The hot lead is dumped into the cold water, and the temperature
of the final leadwater mixture is 28.8 C.

qPb + qH2O = 0
(mcT)Pb + (mc T) H2O = 0
(150.0g)(cPb)(28.8 100C) + (50.0g(4.18J/gC)(28.8
22.0C) = 0
-10680gC (cPb) + 1421.2 J = 0
cPb = 0.133 J/gC (specific heat of Pb.).
How to convert to heat capacity?
Multiply by Molar mass (g/mol) = ? J/molC

Given: specific heat of water: 4.18 J/g C

73

74

Specific Heat of Substances

H2O molecules form H-bonds is an important part of the reason why

water has a large specific heat value. Energy is stored in hydrogen
bonds, particularly strong intermolecular interactions.

High Specific Heat of Compounds

Because of their greater complexity at the molecular level,
compounds generally have more ways of storing internal energy
than do the elements; they tend to have higher specific heats.

Can we explain why

liquid water has a high
specific heat?

H2O for example, has a specific heat that is more than 30 times as
great as that of Pb. A much larger quantity of heat to change the
temperature of a sample of water than of an equal mass of a metal.

76

Thermochemistry
We are going to return to calorimetry
(i.e. bomb-calorimeters) later.

77

Measurement of H
and how can obtain
U from it.

78

Thermodynamic Standard States

Standard Heat of Reaction and

Standard Molar Enthalpy of
Formation

e.g. Ho

Hreaction = Hrxn
Hformation = Hf

Thermodynamic standard state condition of a

substance is its most stable form under 1
standard pressure (1 atm, strictly 1 bar) and
at some specified temperature (normally
298K but could be some other T).
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80

Thermodynamic Standard
States of Matter at a specified T.

Thermodynamic Standard

For pure substances in their liquid or solid phase

the standard state is the pure liquid or solid.

State e.g. Ho

For gases the standard state is the gas at 1.00 atm

of pressure.

The o refers to
1 atm or 1 bar
at T (normally 298 K

For gaseous mixtures the partial pressure must be

1.00 atm.

So

Go 81

Thermodynamic Standard State STP

For aqueous solutions the standard state is 1.00 M

concentration.
82

Standard Enthalpy Change for a Reaction, Ho rxn

At 298K and 1 atm, Examples:

H2 (g), Hg (l, silver), C (graphite), S(s, rhombic)
Ethanol (l), H2O (l), CaCO3 (s), CO2(g)

Take note of difference between standard

conditions and the STP = standard
temperature and pressure used for gas
calculations (273K and 1 atm).
83

 Reactants
 Products
 The Horxn refers to the H when the
specified number of moles reactants, all at
standard states, are converted completely
to the specified number of moles of
products, at all standard states.
 Horxn = standard heat of reaction.
84

Br2(l)
Br2(g)
Hf = 30.91 kJ

Standard Molar
Enthalpies of
Formation, Hfo

Although we can obtain bromine in either

the gaseous or liquid state at 298.15 K, Br2
(l) is the most stable form. Br2(g) if
obtained at 298.15 K and 1 bar pressure,
immediately condenses to Br2(l).

Liquid bromine vaporizing

85

Standard Molar Enthalpies of

Formation, Hfo

Copyright 2011 Petrucci, Pearson

Canada Inc.

Standard Molar Enthalpies of Formation,

Hfo

The enthalpy for the reaction in which one mole of

a substance is formed from its constituent
elements.

Have been determined for many substances and

are tabulated.

The standard molar enthalpy of formation for

MgCl2 is:

Standard molar enthalpies of elements in their

most stable forms at 298.15 K and 1.000 atm are
zero.

Mg (s ) + Cl 2( g ) MgCl 2(s ) + 6418

. kJ
HfoNa(s) = 0 HfoBr (l) = 0 HfoO2 (g) = 0
but HfoNa+ (aq) 0 and HfoNa (g) 0

H of MgCl 2 ( s ) = 6418
. kJ / mol
Take note! 1 mol MgCl2 is formed.

87

88

Standard Molar Enthalpies of

Formation, Hof, 298 K

Hfo Calculation: Practice Exercise

The standard molar enthalpy of formation of Ca(OH)2 (s)
is 946 kJ/mol.
Write the thermochemical equation.
The standard molar enthalpy of formation for sulfuric
acid(l) is -1281 kJ/mol. Write the equation for the
standard formation of sulfuric acid.

Ca(s) +O2(g) + H2(g) Ca(OH)2 (s)

H = -987 kJ/mol

H = -987 kJ mol-1 = Hf Ca(OH)2 Hf Ca(s) Hf O2(g) Hf H2(g)

You do it!

89

90

Practice Exercises:
Write the balanced chemical equations
whose H0reaction is equal to the H0f for
each of the following substances:
H2S(g)
PbCl2(s)
Atomic Oxygen (g)
Benzoic Acid C6H5COOH(s)
H2O2(l)
N2O5(g)
Ozone, O3 (g)
91

Petrucci, General Chemistry:

Chapter 7

Most cases: Hformation < 0

Standard Enthalpy of Formation

number of carbons

FIGURE 7-18

Some standard enthalpies of formation at 298.15 K

Copyright 2011
Pearson Canada Inc.

Copyright 2011
Pearson Canada Inc.

General Chemistry: Chapter 7

Standard Enthalpies of Reaction

H = pHf(products) rHf(reactants) (7.21)

Dissociation into
elemental forms

FIGURE 7-20

Hoverall = 2HfNaHCO3+
HfNa2CO3
+ HfCO2 +

Hf H2O

Computing heats of reaction from standard enthalpies of formation

Copyright 2011
Pearson Canada Inc.

General Chemistry: Chapter 7

FIGURE 7-21

Diagramatic representation of equation (7.21)

Petrucci, General Chemistry:
Chapter 7

Calculation of Ho rxn

CS2 (l)+3 Cl2(g)

What is calculated Ho rxn for the following

reaction based from the tabulated Ho f values?
o
.CS2 (l)+3 Cl2(g) CCl4 (l) + S2Cl2 (l) H rxn =?
Determine the enthalpy of formation of CCl4(g)
at 25oC and 1 atm.
CH4 (g)+ 4Cl2(g) CCl4 (g) + 4HCl(g)
Ho rxn = -397.3kJ

CCl4 (l) + S2Cl2 (l)

Ho rxn =?

CS2 (l) +89.70 kJ/mol

HCl(g) - 92.31 kJ/mol
CCl4 (l) - 135.4 kJ/mol
S2Cl2 (l) - 18.40 kJ/mol

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CH4 (g)+ 4Cl2(g)

CCl4 (g) + 4HCl(g)

Ho rxn = -397.3kJ
Ho formation (CCl4) = ?

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Standard Molar Enthalpies of

Formation, Hfo
Example: Calculate the Hrxn for the reaction of
one mole of H2(g) with one mole of F2(g) to form
two moles of HF(g) at 25oC and 1 atm. Given Hfo
HF = -271 kJ/mol

Ho f values (1 atm, 298K)

H 2(g) + F 2(g)

HCl(g) - 92.31 kJ/mol

CH4 (g) - 74.81 kJ/mol

2HF(g)

Find the Horxn = ?

But we know that for standard enthalpy of formation:

H 2(g) + F 2(g) HF(g) Hof HF = -271 kJ

CCl4 (g) - 102.9 kJ/mol

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Standard Molar Enthalpies of

Formation, Hfo

Standard Molar Enthalpies of

Formation, Hfo

H 2(g) + F 2(g) HF(g)

Ho

rxn

= {Ho f

Ho

rxn

= {-271 kJ/mol} {0 + 0} = -271 kJ/mol

HF(g)_

} - {1/2Ho f

H2(g)

+ 1/2Hof

100

F2(g)}

Example: Calculate the enthalpy change

for the reaction in which 30.0 g of
aluminum reacts with oxygen to form Al2O3
at 25oC and 1 atm.
You do it!

H 2(g) + F 2(g) 2HF(g)

2 mol HF x Ho
Therefore, Ho

rxn

rxn(in

Ho

rxn

=?

Given:

kJ/mol)

H of Al2 O3 = 1676 kJ / mol

Al (27 g/mol))

= 2 mol x (-271 kJ/mol) = -542 kJ

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OR if we simplify the equation to give 1

mole product.

Standard Molar Enthalpies of

Formation, Hfo

4 Al(s) + 3 O2(g ) 2 Al2 O 3(s)

4 Al(s) + 3 O2(g) 2 Al2 O3(s)

2 Al(s) + 3/2 O 2(g)

1 mol Al 2 mol Al2 O3

27.0 g Al
4 mol Al
1676 kJ
= 931 kJ
1 mol Al2 O3

1 Al2 O 3(s)

1 mol Al 1 mol Al 2 O 3

27.0 g Al
2 mol Al
1676 kJ
= - 931 kJ
1 mol Al2 O3

? kJ = 30.0 g Al

? kJ = 30.0 g Al

103

Practice Exercise:
3Mg + N2  Mg3N2

104

Practice Exercise:
3Mg + N2  Mg3N2

We burn 9.00 g of pure Mg (24.3g/mol) in

excess N2 at constant atmospheric
pressure to form pure magnesium nitride.
Then we bring the reaction mixture back to
25oC.
In this process, 85.40 kJ of heat is
released. What is the standard molar
enthalpy of formation of magnesium
nitride?
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We burn 9.00 g of pure Mg (24.3g/mol) in excess N2 at constant

atmospheric pressure to form pure magnesium nitride.
Then we bring the reaction mixture back to 25oC.
In this process, 85.40 kJ of heat is released. What is the standard
molar enthalpy of formation of magnesium nitride?

(-85.40 kJ/ 0.370 mol Mg)* 3 mol Mg/1 mol Mg3N2)= -692 kJ/mol Mg3N2

106

3Mg(s) + N2(g)  Mg3N2 (s)

9.00 g Mg
*
24.3g/mol Mg

There are also Hformation for ions.

1mol Mg3N2 = 1.23 x10-1 mol Mg3N2

3mol Mg

- 85.40 kJ
=
1.23 x10-1 mol Mg3N2

Hfo for H+ = 0 but it is NOT zero for other

ions. Remember this!
Now we will solve, the Hrxno for ionic
reactions. Take note that you must use
the net ionic equations for this case.

-694 kJ/mol M3N2

Since Ho rxn = Hof Mg3N2 = -694 kJ/mol

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When 20.0 ml of 0.10M Ba(NO3)2(aq) and

12.0 ml of 0.10 M Na2CrO4(aq) are mixed

Ba2+ + CrO4 2-  BaCrO4(s)

2.0 mmol

together in a beaker, a yellow precipitate is

formed. Assume that both solutions are
initially at 25oC (and Patm pressure = 1atm),
and the final volume of the solution is 32.0ml.
Calculate:

1.2 mmol

1.2 mmol

Horxn

= Hof for BaCrO4(s) - Hof Ba2+

(aq) - Hof CrO42- (aq)
= -1446.0 + 537.64 + 881.5 = -26.86 kJ/mol.

the Horxn.
Total heat in joules, qrxn, evolved in the
precipitation.

qrxn/no.of mol limiting reactant = Horeaction

qrxn
= Horeaction * nLR
qrxn
=(-26.86kJ/mol)(1000J/kJ)(1.2x10-3 mol)
qrxn
= -32.2 J of heat is evolved

Hof for BaCrO4(s):

1446.0 kJ/mol
Hof Ba2+ (aq): -537.64 kJ/mol
Hof CrO42- (aq): -881.5kJ/mol
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Table 7.3 Some Standard

Enthalpies of Formation of Ions
in Aqueous Solutions.

110

Practice Example A and B/p274

Petrucci
A. Given:

Hof, AgI = -61.84 kJ mol-1

Hof, Ag+ = +105.6 kJ mol-1
Hof, I- = -55.19 kJ mol-1

Calculate the standard enthalpy change for

the precipitation of silver iodide.
B. Given: The standard enthalpy change for
the precipitation of silver carbonate is -39.9
kJ mol-1. What is the Hof, Ag2CO3 ?
111

Additional Exercises

112

Hesss Law; Petrucci 71/p287

Hesss Law and various applications

Born-Haber-Fajans Cycle.
We will discuss this next meeting.

113

114

Hesss Law; Petrucci 73/p287

115

Now, do your problem set.

Remember, you cannot afford not to
devote at least an hour for studying Chem
17 everyday.
Trust me on this! Or else you will be
overwhelmed with materials come exam
time.

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