The Nature of Energy

•Thermochemistry is the study of energy changes that

accompany chemical reactions.
•Energy is the capacity to do work or to transfer heat.
Chapter 5 •Work is the product of force applied to an object over a
distance:
Thermochemistry w = F ×d
So, it takes work to climb stairs. It requires work to separate
twp oppositely charged ions.
•Heat is the transfer of energy between two objects with
different temperatures.

The Nature of Energy The Nature of Energy

Kinetic Energy and Potential Energy
• Kinetic energy is the energy of motion:
1 between two oppositely charged particles, Q1 and Q2, a
Ek = mv 2
2
• Potential energy is the energy an object possesses by
virtue of its position.
• Potential energy can be converted into kinetic energy.
Example: a bicyclist at the top of a hill.
Kinetic Energy and Potential Energy
• Electrostatic potential energy, Ed, is the attraction
distance d apart:
κQ Q
Ed = 1 2
d
• The constant κ = 8.99 × 109 J-m/C2.
• If the two particles are of opposite charge, then Ed is the
electrostatic repulsion between them.

The Nature of Energy The Nature of Energy

Units of Energy Systems and Surroundings
• SI Unit for energy is the joule, J: • System: part of the universe we are interested in.
• Surroundings: the rest of the universe.
1 2 1
mv = (2 kg )(1 m/s ) • Heat and work are the two ways of transferring energy
2
Ek =
2 2 between system and surroundings.
= 1 kg • m 2 /s 2 = 1 J
We sometimes use the calorie instead of the joule:
1 cal = 4.184 J (exactly)
A nutritional Calorie:
1 Cal = 1000 cal = 1 kcal

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 The First Law of
Thermodynamics
Internal Energy Relating ΔE to Heat and Work
• Internal Energy: total energy of a system. It is the sum of • Energy cannot be created or destroyed.
kinetic and potential energies. • Energy of (system + surroundings) is constant.
• Cannot measure absolute internal energy. • Any energy transferred from a system must be transferred
• Change in internal energy, to the surroundings (and vice versa).
• From the first law of thermodynamics:
ΔE = Efinal − Einitial when a system undergoes a physical or chemical change, the
change in internal energy is given by the heat added to or
absorbed by the system plus the work done on or by the
system: ΔE = q + w

The First Law of

Thermodynamics

PV work
• Chemical reactions can absorb or release heat.
• However, they also have the ability to do work.
Exothermic and Endothermic
• For example, when a gas is produced, then the gas
Processes
produced can be used to push a piston, thus doing work.
• Endothermic: absorbs heat from the surroundings.
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
• Exothermic: transfers heat to the surroundings.
• The work performed by the above reaction is called
pressure-volume work. • An endothermic reaction feels cold.
• When the pressure is • An exothermic reaction feels hot.
constant,
w = − PΔV

2
 State Functions
• State function: depends only on the state of the system. State Functions
The state is defined by specifying such properties as
temperature, pressure, amounts of each component, and
physical form. Internal energy is a state function.

Enthalpy Enthalpy
• Enthalpy, H:
H = E + PV
• Enthalpy is a state function.
• If the process occurs at constant pressure, enthalpy
change defines heat transferred between the system and
surroundings.
ΔH = q p
• When ΔH, is positive, the system gains heat from the
surroundings.
• When ΔH, is negative, the surroundings gain heat from
the system.

Enthalpies of Reaction Enthalpies of Reaction

• For a reaction:
ΔH = H final − H initial
• Change in enthalpy depends on state:
= H products − H reactants
H2O(g) → H2O(l) ΔH = -88 kJ
• Enthalpy is an extensive property (magnitude ΔH is • When we reverse a reaction, we change the sign of ΔH:
directly proportional to amount): CO2(g) + 2H2O(g) → CH4(g) + 2O2(g) ΔH = +802 kJ
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ΔH = -802 kJ This can be clearly illustrated by an enthalpy diagram.
2CH4(g) + 4O2(g) → 2CO2(g) + 4H2O(g) ΔH = −1604 kJ CH4(g) + 2O2(g)

There are thermochemical equations – they always refer

to moles of reactants and products and the energy 802 kJ -802 kJ

associated with the reaction is written to the right. Note:

the physical state of each substance must be specified. CO2(g) + 2H2O(g)

3
 Calorimetry
Examples:

Problem 1: The industrial preparation of CS2 is direct
combination of the elements.
4C(s) + S8(s) Æ 4 CS2(l) ΔH = 358.8 kJ
How much heat is absorbed in the reaction of 20.0 g of
carbon with excess sulfur?
Problem 2: When 36.0 g of Al reacts with excess Fe2O3,
565 kJ of heat is evolved. The reaction is
2Al(s) + Fe2O3(s) Æ 2 Fe(s) + Al2O3(s) ΔH = ?
Determine the change in enthalpy for this reaction.
Heat Capacity and Specific Heat
• Calorimetry = measurement of heat flow.
• Calorimeter = apparatus that measures heat flow.
• Heat capacity = the amount of energy required to raise
the temperature of an object (by one degree).
• Molar heat capacity = heat capacity of 1 mol of a
substance.
• Specific heat = specific heat capacity = heat capacity of 1
g of a substance.
q = (specific heat )× (grams of substance)× ΔT

Examples: Constant Pressure Calorimetry

Problem1: What amount of heat has
been absorbed by 1.00 kg of water if
its temperature increases from 18.22 to
22.73 oC? The specific heat of water is
4.184 J/g oC.
• Atmospheric pressure is constant!
ΔH = qP
qrxn = −qsoln = −(specific heat of solution )
× (grams of solution ) × ΔT

Problem2: A coffee-cup calorimeter,

of the type you will use in lab exp.8,
contains 162 g of water at 22.4 oC. A
75 g block of iron is heated to 99.8 oC
and placed in the water in the
calorimeter. The contents of the
calorimeter come to a temperature of
26.1 oC. What is the specific heat of
iron?

Calorimetry
Bomb Calorimetry (Constant Volume
Example:
Calorimetry)
Problem: The reaction of Ba(OH)2·8H2O(s) with
NH4NO3(s) was performed in a calorimeter. When a • Reaction carried out under
31.6 g sample of Ba(OH)2·8H2O reacted with a slight constant volume.
excess of NH4NO3, the temperature fell from 22.4 oC • Use a bomb calorimeter.
to -16.1 oC. The heat capacity of the resulting mixture • Usually study combustion.
and calorimeter was 161.9 J/oC. Determine ΔH for the • Measure the change of
reaction: internal energy.
Ba(OH)2·8H2O(s) + 2NH4NO3(s) Æ Ba(NO3)2(s) + 2
NH3 (aq) + 10 H2O(l) ΔE = qrxn = −Ccal × T

4
 Hess’s Law
Example: • Hess’s law: if a reaction is carried out in a number of
Problem: A 0.3361 g sample of B2H6(g) was reacted with steps, ΔH for the overall reaction is the sum of ΔH for
excess oxygen in a bomb calorimeter whose heat capacity is each individual step.
4.106 kJ/oC. The temperature increased by 6.340 oC.
Calculate ΔE for the reaction.
B2H6(g) + 3O2(g) Æ B2O3(s) + 3H2O(l)
• For example:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ΔH = -802 kJ
2H2O(g) → 2H2O(l) ΔH = -88 kJ
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)ΔH = -890 kJ

Example:
Hess’s Law Problem: Determine ΔH for the following reaction:
C2H2(g) + 5N2O(g) Æ 2CO2(g) + H2O(g) + 5N2(g)
Values of ΔH for the combustion of acetylene and for the
formation of nitrous oxide from the elements have been
Note that: determined.
ΔH1 = ΔH2 + ΔH3 2 C2H2(g) + 5 O2(g) Æ 4 CO2(g) + 2H2O(g) ΔH = -2512kJ
N2(g) +1/2 O2(g) Æ N2O(g) ΔH = +81.6 kJ

Note: in using Hess’s law remember:

1: If an equation is multiplies by a factor, ΔH is also
multiplied by the same factor.
2: If an equation is reversed, the sign of ΔH changes.
3: All substances not appearing in the desired equation must
cancel.

Enthalpies of Formation Enthalpies of Formation

• If 1 mol of compound is formed from its constituent
elements, then the enthalpy change for the reaction is
called the enthalpy of formation, ΔHf .
• Standard conditions (standard state): 1 atm and 25 oC
(298 K).
• Standard enthalpy of formation ΔHof : 1 mol of
compound is formed from its constituent elements in
their standard states.
• If there is more than one state for a substance under
standard conditions, the more stable one is used.
• Standard enthalpy of formation of the most stable form of
an element is zero.

5
 Using Enthalpies of Formation of
Calculate Enthalpies of Reaction
• We use Hess’ Law to calculate enthalpies of a reaction
from enthalpies of formation. For a reaction:
Example: Find the enthalpy change for the following
ΔH °rxn = ∑ nΔH °f (products ) − ∑ mΔH °f (reactants ) reaction using a table of standard enthalpies of formation.
2H2S(g) + 3 O2(g) Æ 2H2O(l) + 2SO2(g)
• This can be clearly illustrated by the enthalpy diagram:
constituent elements

Forming products
Decompose

products

reactants

Foods and Fuels

Foods
• Fuel value = energy released when 1 g of substance is
burned.
• 1 nutritional Calorie, 1 Cal = 1000 cal = 1 kcal.
• Energy in our bodies comes from carbohydrates and fats
(mostly).
• Intestines: carbohydrates converted into glucose:
C6H12O6 + 6O2 → 6CO2 + 6H2O, ΔH = -2816 kJ
• Fats break down as follows:
2C57H110O6 + 163O2 → 114CO2 + 110H2O, ΔH = -75,520 kJ

Foods and Fuels Foods and Fuels

Foods Fuels
• Fats: contain more energy; are not water soluble, so are • In 2000 the United States consumed 1.03 × 1017 kJ of
good for energy storage. fuel.
• Most from petroleum and natural gas.
• Remainder from coal, nuclear, and hydroelectric.
• Fossil fuels are not renewable.

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 Foods and Fuels
Fuels
• Fuel value = energy released when 1 g of substance is
Foods and burned.
Fuels • Hydrogen has great potential as a fuel with a fuel value of
142 kJ/g.

End of Chapter 5

Recommended Exercises: 15, 22, 23, 26,

27, 30, 32, 33, 36, 37, 42, 43, 52, 53, 54,
57, 62, 63, 66, 67, 72, 77