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Chapter 5
Principles of Reactivity: Energy and
Chemical Reactions

Chapter Outline:

5.1 Energy: basic principles

5.2 Specific heat capacity: heating and cooling
5.3 Energy & changes of state
5.4 The 1st law of thermodynamics
5.5 Enthalpy changes for chemical reactions
5.6 Calorimetry
5.7 Enthalpy Calculations
5.8 Product- or reactant-favoured reactions &
thermochemistry

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Energy & Chemistry

• Burning peanuts supply • Burning sugar (sugar

sufficient energy to boil reacts with KClO3, a
a cup of water. strong oxidizing agent)

The Nature of Energy

Energy: The capacity to do work or to produce heat.

 Temperature reflects random motions of particles,

therefore related to kinetic energy of the system.

 Heat involves a transfer of thermal energy between

two objects due to a temperature difference

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Types of Energy

Potential Kinetic

Potential Energy
due to position or composition
(can be converted to work)
Examples:
Chemical potential energy: resulting from attractions among
electrons and atomic nuclei in molecules

Gravitational energy: such as that of a ball held above the floor or

that of water at the top of a waterfall

Electrostatic energy: such as positive and negative ions a small

distance apart

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Potential Energy on the
Atomic Scale

• Positive and negative

particles (ions) attract
one another.
• The weaker the bonds,
the higher the potential
energy and ability to do
work.
NaCl — composed of Na+
and Cl- ions.

Kinetic Energy
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due to motion of the object

KE = ½ mv 2
(m = mass, v = velocity)
Examples:
Thermal energy: of atoms, molecules, or ions in motion at the
submicroscopic level according to Kinetic-Molecular
Theory
Mechanical energy: of an object like a moving baseball or car

Electric Energy: of electrons moving through a conductor

 Sound: corresponding to compression and expansion of the spaces

between molecules

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Law of Conservation of Energy

Energy can be converted from one form to another, but can
neither be created nor destroyed.
(Euniverse is constant)

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Potential & Kinetic Energy

Zumdahl, Figure 6.1

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State Function

State Function: A property that is independent of the pathway

Chang, Figure 6.4

Potential energy of hiker 1 and

hiker 2 is the same even though Brown & Lemay, Figure 5.10

they took different paths. work and heat are not state functions

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For a given reaction:
∆H along one path = ∆H along another path

• This equation is valid because ∆H is

a STATE FUNCTION
• These depend only on the state of
the system and not how it got there.
• V, T, P, energy — and your bank
account!
• Unlike V, T, and P, one cannot
measure absolute H. Can only
measure ∆H.
• Note: work and heat are not state
functions
Brown & Lemay, Figure 5.21

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Internal Energy

 PE + KE = Internal energy (E or U)

 Internal energy of a chemical system depends on:

 number of particles
 type of particles
 temperature

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Thermodynamics

 Thermodynamics is the science of heat (energy) transfer.

Heat energy is associated with

molecular motions.

 Heat transfers until thermal equilibrium is established.

 ∆T measures energy transferred.

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System and Surroundings

• SYSTEM
– The object under study
• SURROUNDINGS
– Everything outside the
system

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Directionality of Heat Transfer

• Heat always transfer from hotter object to cooler one.

• EXOthermic: heat transfers from SYSTEM to SURROUNDINGS.

T(system) goes down

T(surr) goes up

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Combustion of Methane

CH4(g) + 2O2(g)  2H2O(g) + CO2(g) + energy (heat)

PEreactants > PEproducts

Zumdahl, Figure 6.2

The bonds in the products are stronger than those of reactants.

more energy is released by forming the new bonds in the products than is
consumed to break the bonds in the reactants.

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Directionality of Heat Transfer
• Heat always transfers from hotter object to cooler one.
• ENDOthermic: heat transfers from SURROUNDINGS to the
SYSTEM.

T(system) goes up
T (surr) goes down

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N2(g) + O2(g) + energy (heat)  2NO(g)

PEreactants < PEproducts

Zumdahl, Figure 6.3

The bonds in the products are weaker than those of reactants.

less energy is released by forming the new bonds in the products than is consumed to
break the bonds in the reactants.

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Heat Capacity
Heat Capacity: The heat required to raise an object’s
temperature by 1 ˚C.

q = C ´ DT
q = heat lost or gained (J)
 J 
C = Heat capacity of an object  
 C or K 
DT = Tfinal  Tinitial is the temperature change (°C or K)

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Heat/Energy Transfer
No Change in State

q transferred = (specific heat capacity)(mass)(∆T)

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Specific Heat Capacity

How much energy is transferred due to T
difference?
The heat (q) “lost” or “gained” is related to
 sample mass
 change in T and
 specific heat capacity
q = m C DT
q = heat lost or gained (J) m = mass of substance (g)
C = the specific heat capacity of a compound  J 
 g ´ C or K 
 
DT = Tfinal  Tinitial is the temperature change (°C or K)

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Does it matter if we calculate a temperature change in Kelvin or

degrees Celcius?

let Ti = 25.0 °C and Tf = 50.0 °C

Recall that DT = Tf –Tin

Tf = 50.0 °C = 50.0 °C + 273.2 = 323.2 K

–Ti =  25.0 °C =  (25.0 °C + 273.2) =  298.2 K

DT = 25.0 °C DT = 25.0 K
The are the same!

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Specific Heat Capacity

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Exercise
If 25.0 g of Al cool from 310 oC to 37 oC, how many joules
of heat energy are lost by the Al?

heat gain/loss = q = (specific heat capacity)(mass)(∆T)

Notice that the negative sign on q signals heat “lost by” or

transferred OUT of Al.

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Exercise

• Use heat transfer as a way to find specific heat capacity, s

• 55.0 g Fe at 99.8 ˚C
• Drop into 225 g water at 21.0 ˚C
• Water and metal come to 23.1 ˚C
• What is the specific heat capacity of the metal (CFe)?

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Answer 27

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Heat/Energy Transfer
With Change in State

Changes of state involve energy (at constant T)

Ice + 333 J/g (heat of fusion) -----> Liquid water
q = (heat of fusion)(mass)

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Heating/Cooling Curve
Note that T is constant as
ice melts

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Heat and Changes of States
What quantity of heat is required to melt 500. g of ice and
heat the water to steam at 100 oC?

Heat of fusion of ice = 333 J/g

Specific heat of water = 4.2 J/g•K
Heat of vaporization = 2260 J/g

+333 J/g +2260 J/g

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Answer

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Heat Energy Transfer in a
Physical Process
CO2 (s, -78 oC) ---> CO2 (g, -78 oC)
Heat transfers from surroundings to system in endothermic process.
Two things have happened!
1. Gas molecules have higher kinetic energy.
2. Also, WORK is done by the system in pushing aside the atmosphere.

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Work

F
P = or F = P x A
A
Work = F x d
= F x Dh
= P x A x D h
= P x DV
W system = - P x DV

Zumdahl, Figure 6.4

Work done by the system on the surroundings: negative

Work done by the surroundings on the system: positive

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Exercise
A certain gas expands in volume from 2.0 L to 6.0 L at constant
temperature. Calculate the work done by the gas if it expands (a)against
a vacuum and (b) against a constant pressure of 1.2 atm.
Answer:

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First Law of Thermodynamics

heat energy transferred

∆U = q + w work

energy
change

Energy is conserved!

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heat transfer in heat transfer out
(endothermic), +q (exothermic), -q

SYSTEM

∆U = q + w

w transfer in w transfer out

(+w) (-w)

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Exercise
(1) Calculate ΔU for an endothermic process where 15.6kJ of heat
flows but the system has done 1.4 kJ of work on the surroundings:

(2) Calculate ΔU for an exothermic process where 15.6kJ of heat

flows and where 1.4 kJ of work is done on the system:

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Enthalpy
Most chemical reactions occur at constant P, so
Heat transferred at constant P = qp
qp = ∆H where H = enthalpy

and so ∆U = ∆H + w (and w is usually small)

∆H = heat transferred at constant P ≈ ∆U
∆H = change in heat content of the system
∆H = Hfinal - Hinitial

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Enthalpy

∆H = Hfinal - Hinitial

If Hfinal > Hinitial then ∆H is positive

Process is ENDOTHERMIC

If Hfinal < Hinitial then ∆H is negative

Process is EXOTHERMIC

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Using Enthalpy
H2(g) + 1/2 O2(g) --> H2O(l) + 286 kJ
Exothermic reaction : heat is a “product” and ∆H = – 286 kJ
Making liquid H2O from H2 + O2 involves two exothermic steps.

H2 + O2 gas
H2O vapor Liquid H2O

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Enthalpy and Hess’s Law

Making H2O from H2 involves two steps.

H2(g) + 1/2 O2(g) ---> H2O(g) + 242 kJ
H2O(g) ---> H2O(liq) + 44 kJ
-----------------------------------------------------------------------
H2(g) + 1/2 O2(g) --> H2O(liq) + 286 kJ
Example of HESS’S LAW—

When reactants are converted to products, the change in

enthalpy is the same whether the reaction takes place in one step
or in a series of steps.

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Hess’s Law

Forming H2O can occur in a

single step or in a two steps.
∆Htotal is the same no matter
which path is followed.

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Exercise
Calculate the enthalpy of formation of methane, CH4 from its elements
according to the equation
C(s) + 2H2(g)  CH4(g) ΔH = ?
from the following data:
(a) C(s) + O2(g)  CO2(g) Δ H = - 393.5 kJ
(b) H2(g) + ½O2(g)  H2O(l) Δ H = -285.8 kJ
(c) CH4(g) + 2O2(g)  CO2 (g) + 2H2O(l) Δ H = -890.3 kJ

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State Function

State Function: A property that is independent of the pathway

Chang, Figure 6.4

Potential energy of hiker 1 and

Brown & Lemay, Figure 5.10
hiker 2 is the same even though
they took different paths. work and heat are not state functions

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For a given reaction:
∆H along one path = ∆H along another path

• This equation is valid because ∆H is

a STATE FUNCTION
• These depend only on the state of
the system and not how it got there.
• V, T, P, energy — and your bank
account!
• Unlike V, T, and P, one cannot
measure absolute H. Can only
measure ∆H.
• Note: work and heat are not state
functions
Brown & Lemay, Figure 5.21

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Standard Enthalpy

Most ∆H values are labeled ∆Ho

Measured under standard conditions
P = 1 atm
Concentration = 1 mol/L
with all species in standard states
e.g., C = graphite and O2 = gas

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Standard Enthalpy of Formation
Standard enthalpy of formation, (DHfº ):
The heat change that results when one mole of a compound is formed
from its elements with all substances in their standard states
See Appendix L

The superscript “o” represents standard-state conditions

The subscript “f “ stands for formation.
By convention, the standard enthalpy of formation of any element in its
most stable from is zero.
Ex.1: DHfº (O2) = 0, but DHfº (O3)  0
Since molecular oxygen (O2) is more stable than the other form of
oxygen, ozone (O3).
Ex.2: DHfº (C, graphite) = 0, but DHfº (C, diamond)  0

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Using Standard Enthalpy Values
Calculate the heat of combustion of methanol,
i.e., ∆Horxn for

CH3OH(g) + 3/2 O2(g) --> CO2(g) + 2 H2O(g)

∆Horxn = ∆Hfo (products) - ∆Hfo (reactants)

∆Horxn = ∆Hfo (CO2) + 2 ∆Hfo (H2O) - {3/2 ∆Hfo (O2) + ∆Hfo(CH3OH)}

= (-393.5 kJ) + 2 (-241.8 kJ) - {0 + (-201.5 kJ)}
∆Horxn = -675.6 kJ per mol of methanol

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Enthalpy Values
Depend on how the reaction is written and on phases of
reactants and products

H2(g) + 1/2 O2(g) --> H2O(g)

∆H˚ = -242 kJ
2 H2(g) + O2(g) --> 2 H2O(g)
∆H˚ = -484 kJ
H2O(g) ---> H2(g) + 1/2 O2(g)
∆H˚ = +242 kJ
H2(g) + 1/2 O2(g) --> H2O(liquid)
∆H˚ = -286 kJ

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Exercise
Calculate the standard enthalpy of reaction for the following:
2Al (s) + Fe2O3 (s)  Al2O3(s) + 2Fe(s)

Solution:
 DHrxn° = npDHf(products)  nrDHf(reactants)

 where DHf for Al (s = 0

 DHf for Fe2O3 (s) = - 826 kJ/mol
 DHf for Al2O3(s) = -1676 kJ/mol
 DHf for Fe(s) = 0

 Therefore,

DHrxn° = (DHf (Al2O3(s)) + [2DHf(Fe(s))])  ( [2DHf(Al (s) )] + (DHf ( Fe2O3 (s)))

= (- 1676 kJ + 0) – (0 – 826 kJ/mol) = - 850 kJ/mol

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Constant Pressure Calorimetry

Used to determine the changes in

enthalpy for reactions occurring in
solution
Device: Coffee-Cup Calorimeter

At constant pressure:

q = qp = DH

Zumdahl, Figure 6.5

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Constant Volume Calorimetry
DE = q + w
at constant
= q - P DV
volume
=q
= qv

Device: Bomb Calorimeter

Chang, Figure 6.8

Not always convenient to use, especially in the introductory

chemistry laboratory

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Calorimetry
Measuring Heats of Reaction

Some heat from reaction warms

water
qwater = C water x mass water x ∆T

Some heat from reaction warms

“bomb calorimeter”
qbomb = (heat capacity, J/K) x ∆T

Total heat evolved = qtotal = qwater + qbomb

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Exercise
1.435 g of naphthalene (C10H8) was burned in a bomb calorimeter.
Consequently, the temperature of the water rose from 20.17 ºC to 25.84
ºC. If the mass of water surrounding the calorimeter was exactly 2000 g
and the heat capacity of the bomb calorimeter was 1.80 kJ/ º C,
calculate the molar heat of combustion of naphthalene.
Solution:

qtotal = qwater + q bomb + qreaction = 0

qreaction = - (qwater + q bomb)

qwater = m water Cwater DT
q bomb = Cbomb DT

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