Chapter 5

Thermochemistry
 Thermochemistry
• The study of energy and its transformation in
chemical reaction

2Al2O3 +E 4Al + 3O2 Charcoal + O2 CO2 + H2O+E

 5.1 the nature of energy
• Energy
The ability to do work or transfer heat.
– Work: Energy used to cause an object that has
mass to move.
– Heat: Energy used to cause the temperature of an
object to rise.
 Kinetic Energy
• Energy an object possesses by virtue of its
motion.
1
EK =  mv2
2
PRACTICE EXERCISE
What is the kinetic energy, in J, of
(a) an Ar atom moving with a speed of 650 m/s,
(b) a mole of Ar atoms moving with a speed of 650 m/s? (Hint: 1 amu = 1.66
 10-27kg)

Answers: (a) 1.4  10-20J, (b) 8.4  103J

 Potential Energy
Energy an object possesses by virtue of its position
or chemical composition.

 Ep = mgh
κ
 Electrostatic potential energy: Eel =  Q1Q2
d
κ = 8.99  109J-m/C2
The lower the energy of a system, the more stable it is

Eg. Electron on 3p orbital is easier to be removed than the

electron on 2p orbital
 Units of Energy

• The SI unit of energy is the joule (J).

kg m2
1 J = 1 
s2
• An older, non-SI unit is still in widespread
use: The calorie (cal).
1 cal = 4.184 J
System and Surroundings

• The system includes the

portion we single out for
study (here, the
hydrogen and oxygen
molecules).
• The surroundings are
everything else (here,
the cylinder and piston).
 System and Surroundings
• Open system
• Closed system
• Isolated system
 Work

• Energy used to move

an object over some
distance.
• w = F  d,
where w is work, F is
the force, and d is the
distance over which
the force is exerted.
Heat

• Energy can also be

transferred as heat.
• Heat flows from
warmer objects to
cooler objects.
 Transferal of Energy

a) The potential energy of this ball of clay is

increased when it is moved from the
ground to the top of the wall.
 Transferal of Energy

a) The potential energy of this ball of clay is

increased when it is moved from the
ground to the top of the wall.
b) As the ball falls, its potential energy is
converted to kinetic energy.
 Transferal of Energy

a) The potential energy of this ball of clay is

increased when it is moved from the
ground to the top of the wall.
b) As the ball falls, its potential energy is
converted to kinetic energy.
c) When it hits the ground, its kinetic
energy falls to zero (since it is no longer
moving); some of the energy does work
on the ball, the rest is dissipated as heat.
 5.2 The First Law of Thermodynamics
• Energy is neither created nor destroyed.
• In other words, the total energy of the universe is a
constant; if the system loses energy, it must be
gained by the surroundings, and vice versa.
 Internal Energy
• The internal energy of a system is the sum of all
kinetic and potential energies of all components of
the system; we call it E.
• By definition, the change in internal energy, E, is the
final energy of the system minus the initial energy of
the system:
E = Efinal − Einitial
Changes in Internal Energy

• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, E = q + w.
 E, q, w, and Their Signs

PRACTICE EXERCISE
Calculate the change in the internal energy of the system for a process in which
the system absorbs 140 J of heat from the surroundings and does 85 J of work
on the surroundings.
 Exchange of Heat between System and
Surroundings

• When heat is absorbed by the system from the

surroundings, the process is endothermic.
 Exchange of Heat between System and
Surroundings

• When heat is absorbed by the system from the

surroundings, the process is endothermic.
• When heat is released by the system to the
surroundings, the process is exothermic.
 State Functions
Usually we have no way of knowing the internal
energy of a system; finding that value is simply
too complex a problem.
 State Functions
• However, we do know that the internal energy of a
system is independent of the path by which the
system achieved that state.
– In the system below, the water could have reached room
temperature from either direction.
 State Functions
• Therefore, internal energy is a state function.
• It depends only on the present state of the system,
not on the path by which the system arrived at that
state.
• And so, E depends only on Einitial and Efinal.
State Functions
State Functions
• However, q and w are not
state functions.
• Whether the battery is
shorted out or is
discharged by running
the fan, its E is the
same.
– But q and w are different
in the two cases.
 5.3 Enthalpy
When a process occurs in an open container,
commonly the only work done is a change in
volume of a gas pushing on the surroundings (or
being pushed on by the surroundings).
Work

We can measure the

work done by the gas if
the reaction is done in a
vessel that has been
fitted with a piston.
w = −PV
(P is constant)
 qP and qV
• Constant pressure
If P-V work is the only work that can be done:
W = -P V
E = qP + w = qP - P V

• Constant volume
W = 0 (V=0)
E = q V
 Enthalpy
• If a process takes place at constant pressure
(as the majority of processes we study do)
and the only work done is this pressure-
volume work, we can account for heat flow
during the process by measuring the enthalpy
of the system.
• Enthalpy is the internal energy plus the
product of pressure and volume:
H = E + PV
 Enthalpy
• When the system changes at constant
pressure, the change in enthalpy, H, is
H = (E + PV)
• This can be written
H = E + PV
 Enthalpy
• Since E = qP + w and w = −PV, we can
substitute these into the enthalpy
expression:
H = E + PV
H = (qP +w) − w
H = qP
• So, at constant pressure the change in
enthalpy is the heat gained or lost.
Endothermicity and Exothermicity

• A process is
endothermic, then,
when H is positive.
Endothermicity and Exothermicity

• A process is
endothermic when
H is positive.
• A process is
exothermic when
H is negative.
SAMPLE EXERCISE 5.3 Determining the Sign of H

Indicate the sign of the enthalpy change, H, in each of the following processes
carried out under atmospheric pressure, and indicate whether the process is
endothermic or exothermic: (a) An ice cube melts; (b) 1 g of butane (C4H10)is
combusted in sufficient oxygen to give complete combustion to CO2 and H2O.
Solution
Solve: In (a) H is positive and the process is endothermic. In (b) H is
negative and the process is exothermic.
 5.4 Enthalpies of Reaction

The change in enthalpy,

H, is the enthalpy of
the products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants
 Enthalpies of Reaction

This quantity, H, is called the enthalpy of

reaction, or the heat of reaction(qrxn).
 The Truth about Enthalpy
1. Enthalpy is an extensive property.
CH4 (g) + 2O2(g) CO2(g) + 2H2O(l) H = -890 KJ

2CH4 (g) + 4O2(g) 2CO2(g) + 4H2O(l) H = -1780 KJ

SAMPLE EXERCISE

How much heat is released when 4.50 g of methane gas is burned in a

constant-pressure system?
 The Truth about Enthalpy
2. H for a reaction in the forward direction is
equal in size, but opposite in sign, to H for
the reverse reaction.
CH4 (g) + 2O2(g) CO2(g) + 2H2O(l) H = -890 KJ

CO2(g) + 2H2O(l) CH4 (g) + 2O2(g) H = 890 KJ

 The Truth about Enthalpy
3. H for a reaction depends on the state of the
products and the state of the reactants.
CH4 (g) + 2O2(g) CO2(g) + 2H2O(l) H1 = -890 KJ

2H2O(l) 2H2O(g) H = +88KJ

CH4 (g) + 2O2(g) CO2(g) + 2H2O(g) H2 =?

H1 < H2

PRACTICE EXERCISE
Hydrogen peroxide can decompose to water and oxygen by the following reaction:

Calculate the value of q when 5.00 g of H2O2(l) decomposes at constant pressure.

Answer: –14.4 kJ

How much heat will be released when 11.8g of iron reacts with excess O 2
according to the following equation?
3Fe + 2O2 Fe3O4 H = -1120.48 kJ

Answer: 78.9 kJ

The complete combustion of propane, C3H8(g), to form H2O(g) and CO2(g) at

constant pressure releases 2043kJ of heat per mole of C 3H8. write a balanced
thermochemical equation for this reaction, and draw an enthalpy diagram
for the reaction.
PRACTICE EXERCISE
Without referring to tables, predict which of the following has the higher enthalpy in
each case: (a) 1 mol CO2(s) or 1 mole CO2(g) at the same temperature, (b) 1mol H2(g)
and 0.5 mol O2(g) at 298K or 1 mol H2O(g) at 298K

Limestone stalactites and stalagmites are formed in caves by the following reaciton:
Ca2+ (aq) + 2HCO3-(aq) CaCO3(s) + CO2(g) + H2O(l)
If 1 mol of CaCO3 forms at 298K under 1 atm pressure, the reaction performs 2.47kJ
of P-V work, pushing back the atmosphere as the gaseous CO2 forms. At the same
time, 38.95 kJ of heat is absorbed from the environment. What are the values of H
and E for this reation
5.5 Calorimetry

Since we cannot know

the exact enthalpy of
the reactants and
products, we measure
H through
calorimetry, the
measurement of heat
flow.
 Heat Capacity and Specific Heat

• The amount of energy required to raise the

temperature of a substance by 1 K (1C) is its
heat capacity.(unit: J-K-1)
• We define specific heat capacity (or simply
specific heat) as the amount of energy
required to raise the temperature of 1 g of a
substance by 1 K.(unit: J-g-1-K-1)
 Heat Capacity and Specific Heat

Specific heat, then, is

heat transferred
Specific heat =
mass  temperature change
q
s=
m  T
SAMPLE EXERCISE

(a) How much heat is needed to warm 250 g of water (about 1 cup) from
22°C (about room temperature) to near its boiling point, 98°C? The specific
heat of water is 4.18 J/g-K. (b) What is the molar heat capacity of water?

Solution
Solve: (a) The water undergoes a temperature change of

T = 98ºC – 22ºC = 76ºC =76 K

q =s m  T
= (4.18 J/g-K)(250 g)(76 K) = 7.9  104J

(b) 1 mol H2O = 18.0 g H2O

From the specific heat given in part (a), we have
PRACTICE EXERCISE
(a) Large beds of rocks are used in some solar-heated homes to store heat.
Assume that the specific heat of the rocks is 0.082 J/g-K. Calculate the
quantity of heat absorbed by 50.0 kg of rocks if their temperature increases
by 12.0°C. (b) What temperature change would these rocks undergo if they
emitted 45 kJ of heat?

Answers: (a) 4.9  105 J, (b) 11 K = 11ºC decrease

Constant Pressure Calorimetry
By carrying out a reaction
in aqueous solution in a
simple calorimeter such as
this one, one can indirectly
measure the heat change
for the system by
measuring the heat
change for the water in
the calorimeter.
Constant Pressure Calorimetry

Because the specific heat

for water is well known
(4.184 J/mol-K), we can
measure H for the
reaction with this
equation:
q = m  s  T
 SAMPLE EXERCISE
When a student mixes 50 mL of 1.0 M HCl and 50 mL of 1.0 M NaOH in a coffee-cup
calorimeter, the temperature of the resultant solution increases from 21.0°C to 27.5°C.
Calculate the enthalpy change for the reaction in kJ/mol HCl, assuming that the
calorimeter loses only a negligible quantity of heat, that the total volume of the
solution is 100 mL, that its density is 1.0g/mL, and that its specific heat is 4.18 J/g-K.
Solution

To express the enthalpy change on a molar basis, we use the fact that the number of
moles of HCl and NaOH is given by the product of the respective solution volumes
(50ml = 0.050 L) and concentrations:

(0.050 L)(1.0 mol/L) = 0.050 mol

Thus, the enthalpy change per mole of HCl (or NaOH) is

 Bomb Calorimetry

Reactions can be
carried out in a sealed
“bomb,” such as this
one, and measure the
heat absorbed by the
water.
 Bomb Calorimetry

• Because the volume in

the bomb calorimeter is
constant, what is
measured is really the
change in internal
energy, E, not H.
• For most reactions, the
difference is very small.
SAMPLE EXERCISE

Methylhydrazine (CH6N2) is commonly used as a liquid rocket fuel. The combustion of

methylhydrazine with oxygen produces N2(g), CO2(g), and H2O(l):

When 4.00 g of methylhydrazine is combusted in a bomb calorimeter, the temperature

of the calorimeter increases from 25.00°C to 39.50°C. In a separate experiment the
heat capacity of the calorimeter is measured to be 7.794 kJ/°C. What is the heat of
reaction for the combustion of a mole of CH6N2 in this calorimeter?

Solution

We can readily convert this value to the heat of reaction for a mole of CH 6N2:
 Hess’s Law

• H is well known for many reactions, and

it is inconvenient to measure H for
every reaction in which we are
interested.
• However, we can estimate H using H
values that are published and the
properties of enthalpy.
Hess’s Law

Because H is a state
function, the total
enthalpy change depends
only on the initial state of
the reactants and the final
state of the products.
Hess’s Law

Hess’s law states that

“If a reaction is carried
out in a series of
steps, H for the
overall reaction will be
equal to the sum of
the enthalpy changes
for the individual
steps.”
 Hess’s Law

CH4 (g) + 2O2(g) CO2(g) + 2H2O(l) H1 = -890 KJ

2H2O(l) 2H2O(g) H2 = +88KJ

CH4 (g) + 2O2(g) CO2(g) + 2H2O(g) H =?

H = H1 + H2 = -890 KJ + 88KJ = -802 KJ

SAMPLE EXERCISE

The enthalpy of reaction for the combustion of C to CO2 is – 393.5 kJ/mol C, and the
enthalpy for the combustion of CO to CO2 is – 283.0 kJ/mol CO:

Using these data, calculate the enthalpy for the combustion of C to CO :

Solution
SAMPLE EXERCISE
Calculate H for the reaction

given the following chemical equations and their respective enthalpy

changes:

Solution
PRACTICE EXERCISE
1. Carbon occurs in two forms, graphite and diamond. The enthalpy of the combustion
of graphite is –393.5 kJ/mol and that of diamond is –395.4 kJ/mol:

Calculate H for the conversion of graphite to diamond:

2. Calculate H for the reaction

given the following information:

Answer: 1. H3 = +1.9 kJ 2. –304.1kJ

 5.7 Enthalpies of Formation
An enthalpy of formation, Hf, is defined as
the enthalpy change for the reaction in which
a compound is made from its constituent
elements in their elemental forms.
Standard Enthalpies of Formation
• Standard enthalpies of formation, Hf, are
measured under standard conditions (25°C and
1.00 atm pressure).
• We define that the enthalpies of the most stable
form of the elements under standard conditions
are zero.
eg. C (graphite) and C (diamond)
I2(s) and I2(g)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)

3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)

3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)

3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• The sum of these
equations is:

C3H8 (g)  3 C(graphite) + 4 H2 (g)

3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)

 Calculation of H
We can use Hess’s law in this way:

H = nH f(products) - mH f(reactants)

where n and m are the stoichiometric

coefficients.
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
H = [3(-393.5 kJ) + 4(-285.8 kJ)] - [1(-103.85 kJ) + 5(0 kJ)]
= [(-1180.5 kJ) + (-1143.2 kJ)] - [(-103.85 kJ) + (0 kJ)]
= (-2323.7 kJ) - (-103.85 kJ)
= -2219.9 kJ
 SAMPLE EXERCISE

1. Using the standard enthalpies of formation listed in Table 5.3, calculate the
enthalpy change for the combustion of 1 mol of ethanol:

Answer: –1367 kJ

2. The standard enthalpy change for the reaction

is 178.1 kJ. From the values for the standard enthalpies of formation of CaO(s)
and CO2(g) given in Table 5.3, calculate the standard enthalpy of formation of
CaCO3(s).
Solution

Solving for gives

8.8 Strengths of Covalent Bonds

• Most simply, the strength of a bond is measured

by determining how much energy is required to
break the bond.
• This is the bond enthalpy.
• The bond enthalpy for a Cl—Cl bond,
D(Cl—Cl), is measured to be 242 kJ/mol.
 Average Bond Enthalpies

• Average bond enthalpies

are positive, because
bond breaking is an
endothermic process.
• average bond enthalpies
are not absolute bond
enthalpies
Eg. the C—H bonds in methane,
CH4, will be a bit different than the
C—H bond in chloroform, CHCl3
 Average Bond Enthalpies

NOTE: These are average

bond enthalpies, not
absolute bond
enthalpies; the C—H
bonds in methane, CH4,
will be a bit different
than the
C—H bond in
chloroform, CHCl3.
 Enthalpies of Reaction

• Yet another way to

estimate H for a
reaction is to compare
the bond enthalpies of
bonds broken to the bond
enthalpies of the new
bonds formed.

• In other words,
Hrxn = (bond enthalpies of bonds broken) 
(bond enthalpies of bonds formed)
 Enthalpies of Reaction

CH4(g) + Cl2(g) 

CH3Cl(g) + HCl(g)

In this example, one

C—H bond and one
Cl—Cl bond are broken; one
C—Cl and one H—Cl bond
are formed.
 Enthalpies of Reaction

So,
Hrxn = [D(C—H) + D(Cl—Cl)  [D(C—Cl) + D(H—Cl)
= [(413 kJ) + (242 kJ)]  [(328 kJ) + (431 kJ)]
= (655 kJ)  (759 kJ)
= 104 kJ
SAMPLE EXERCISE

Using Table 8.4, estimate H for the following reaction (where we explicitly show the
bonds involved in the reactants and products):

Solution

Using Equation 8.12 and data from Table 8.4, we have

 Bond Enthalpy and Bond Length

• As the number of bonds between two atoms

increases, the bond grows shorter and stronger.
• As the number of bonds between two atoms
increases, the bond length decreases and the bond
enthalpy increases.