Chemistry: for

Engineering Students

Chapter 9: Energy and Chemistry

9.1 INSIGHT INTO Energy Use and the World Economy
9.2 Defining Energy
9.3 Energy Transformation and Conservation of Energy
9.4 Heat Capacity and Calorimetry
9.5 Enthalpy
9.6 Hess’s Law and Heats of Reaction
9.7 Energy and Stoichiometry

Mar-16

Chapter-9 1
Chemistry: for
Engineering Students Energy Use and the World Economy
Exponential growth in the use of primary energy sources
MTOE (*)

Global
warming!

(*) Millions of Tons of Oil Equivalent

Mar-16 Chapter-9 2
Chemistry: for
Engineering Students Energy Use and the World Economy
Primary Energy Sources

Oil
14.3
Gas
12.2
% 43.7 Coal
8.7
Nuclear
21.6
Renewable
SPAIN (2013)

Hydropower 2.6 %
Wind power, Solar, Geothermal 6.2 %
Biomass & trash 5.2 %

Mar-16 Chapter-9 3
Chemistry: for
Engineering Students
Defining Energy

What is energy?

Forms of energy Thermodynamics

1 2
mv Kinetic energy
2 Thermodynamics studies all
mgh Gravitational energy changes involved in
potential energy physical and chemical processes
q1q2 Electric
4πε 0 r1 − r2 potential energy Energy Units
Joule (SI unit)
Radiant energy of
ε0E2 electromagnetic waves 1 J ≡ 1 kg m 2 s −2
D(O = O ) Chemical bonds! Calorie (traditional unit)
4.184 J ≡ 1 cal
Mar-16 Chapter-9 4
Chemistry: for
Engineering Students
Defining Energy

The combined kinetic and potential energies of the atoms and

molecules that make up an object constitute its internal energy U.
Molecular Scale
Macroscopic
scale Translational
3
U trans = RT
2
Ukinetic Rotational
3
kJ U rot = RT
298 K ≈ 10 2
mol C2V q(O)=-0.83

Vibrational µ1 O µ2
1 atm ~ (105 Pa) U (P, T) U vib ≈ RT
104.5 0.94 Å
H H

µtotal = 2.2 D
water Chemical
q(H)=0.41

2 kJ
Upotential bonds ≈ −10 δ+
mol H
2.8 Å
2 δ− 2 δ−
Intermolecular O
H
O
H

interactions 1.0 Å δ+ 1.8 Å

δ+

kJ H ∆H=-4.8 kcal/mol
≈ −10 δ+

mol
Chemistry: for
Engineering Students
Energy Transformation and Conservation of Energy
Thermodynamic Vocabulary Types of Systems
Universe = Surroundings ∪ System Isolated ∆U = 0 , ∆m = 0

Closed ∆U ≠ 0 , ∆m = 0
Surroundings

boundary Open ∆U ≠ 0 , ∆m ≠ 0

System Adiabatic q=0

Diathermic q ≠ 0

• Fixed P, T and composition

Equilibrium state
U ( P, T , composition )
• No previous History
• Stable against
small perturbations
Mar-16 Chapter-9 6
Chemistry: for
Engineering Students
Energy Transformation and Conservation of Energy
• Classify the following thermodynamic systems and identify also their
surroundings and boundaries.

Mar-16 Chapter-9 7
Chemistry: for
Engineering Students
Defining Energy
In closed systems, all energy flow is either heat or work

Work is the transfer of Heat is the flow of energy

energy accomplished between two objects, from the
by a force moving a warmer one to the cooler one,
mass some distance w because of a difference in their q
against resistance temperatures.

a) b)

Mar-16 Chapter-9 8
Chemistry: for
Engineering Students
Defining Energy
In closed systems, all energy flow is either heat or work

Pext= 1 atm

w = − Pext ∆V

VA VB

C8H18(l) + 25/2 O2(g) → 8 CO2(g) + 9 H2O(g) + HEAT

The most common type of work in chemical processes is pressure-volume

work (PV-work) exerted by the expansion of the product gases.

Mar-16 Chapter-9 9
Chemistry: for
Engineering Students
Energy Transformation and Conservation of Energy

All the physical and/or chemical changes occurring in nature

are subject to the 1st Law of Conservation of Energy

Heat-work flow
Energy fluxes: q,w sign convention

q, w < 0 q, w > 0 Expansion,

Heating,

U ( PA , TA , comp A )
Reaction,
… U ( PB , TB , compB )

Closed system
Closed system

∆U = U B − U A = q + w
Mar-16 Chapter-9 10
Chemistry: for
Engineering Students
Heat Capacity and Calorimetry

The measurement of heat flow into or out of a system can be

achieved by a set of techniques known as Calorimetry.

A device used to measure a heat

flow q is a calorimeter.

What is the relationship

between q and ∆T ?

Coffee-cup : Constant-pressure
adiabatic calorimeter

Mar-16 Chapter-9 11
Chemistry: for
Engineering Students
Heat Capacity and Calorimetry

The temperature change experienced by an object when it absorbs a certain

amount of heat at constant P is determined by its heat capacity, denoted CP.

Fundamental
Calorimetric q p = CP ∆T = ncP ∆T = mce ∆T
Relationship

Heat capacity Molar heat capacity Specific heat

Extensive Intensive Intensive
magnitude magnitude magnitude
Units: J/K Units: J / K mol Units: J / K g

ce J/(K g) ce J/(K g)

N2(g) 1.04 H2O(l) 4.18

Al(s) 0.90 CH4(g) 2.20
Fe(s) 0.45 CO2(g) 0.84
Hg(l) 0.14 CaCO3(s) 0.82
Mar-16 Chapter-9 12
Chemistry: for
Engineering Students
Heat Capacity and Calorimetry
• A constant-pressure calorimeter contained 75.0 g of water at 16.95°C. A
93.3-g sample of iron at 65.58°C was placed in it, giving a final temperature
of 19.68°C for the system. Calculate the heat capacity of the calorimeter.
Specific heats are 4.184 J/g K for H2O and 0.444 J/g K for Fe.
Chemistry: for
Engineering Students
Heat Capacity and Calorimetry
• The combustion of methylhydrazine (CH6N2), a liquid rocket fuel, 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 (i.e., the calorimeter constant) is measured to be 7.794 kJ/ K.
Calculate the heat of reaction for the combustion of a mole of CH6N2.

Constant-volume
bomb calorimeter

Mar-16 Chapter-9 14
Chemistry: for
Engineering Students Enthalpy
Enthalpy (H) is defined to standardize the thermochemical properties of
chemical reactions (e.g., combustion processes) and phase changes.

Defining Enthalpy: H=U+PV

Simple Syst.
H definition 1st law dw=−PdV Cons. P

∆H = ∆U + ∆ ( PV ) = q + w + ∆ ( PV ) = q − P∆V + ∆ ( PV ) = q p − P∆V + P∆V = q p

Sign convention
∆H=qP
exothermic
P≈ 1atm
endothermic

Mar-16 Chapter-9 15
Chemistry: for
Engineering Students Enthalpy

Enthalpy of Phase Change

system
A phase change is a thermodynamic process
involving two equilibrium states of a simple system A( s ) → A(l )

GAS
Condensation
Evaporation
Endo- Exo-
thermic Sublimation Deposition thermic
LIQUID
processes processes
Melting Freezing
Fusion

SOLID

Mar-16 Chapter-9 16
Chemistry: for
Engineering Students Enthalpy
The enthalpy of phase change measures the
strength of the intermolecular interactions that
are being broken/formed in the process. In other
words, the enthalpy of phase change are related
to intermolecular binding energies.
kJ
kJ ∆ vap H = 40.67
∆ fus H = 6.01 mol
mol
H2O(g)
Intermolecular
interactions are
negligible

H2O(s) H2O(l)
2-3 H-bonds / molecule
4 H-bonds / molecule
Mar-16 Chapter-9 17
Chemistry: for
Engineering Students Enthalpy
A graph of temperature versus amount of heat added is called a heating curve. Inspection of a
heating curve, which can be recorded automatically using modern calorimeters, reveals the
presence of the phase equilibrium and the magnitude of the phase change enthalpies.
0.91 0.92
7.54
6.01 40.67
F Vapor
P=1 atm D E
100 Tb

75

50
Liquid DE : H 2 O(l ) H 2 O(g)
T(oC) 25
B BC : H 2O(s ) H 2O(l )
C
0 Tm
-25 ASolid
0 10 20 30 40 50 60
Added heat (kJ/mol water)

Enthalpy of ∆ fus H = qBC ∆vap H = qDE

phase change
Mar-16 Chapter-9 18
Chemistry: for
Engineering Students Enthalpy
Heat of Reaction and thermochemical Equations
const. P
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) + 802 kJ
const. P
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) ∆rH= −802 kJ

∆rH= −802 kJ / mol CH4 Intensive

form

•Suppose that natural gas is simply pure methane (CH4 ) gas. How does this fuel store
its energy content?

Mar-16 Chapter-9 19
Chemistry: for
Engineering Students Enthalpy
Some classes of chemical reactions are sufficiently common or useful that they
have been assigned their own label for heats of reaction. Tabulated data are
usually given for the standard state (P = 1 bar ~ 1 atm) at 298.15 K (25 oC) of
reactants and products.

Combustion Enthalpy: ∆combH0 is the enthalpy change associated to the

total combustion of a fuel.
15 P =1 bar
C6 H 6(l ) + O 2( g ) T
= 298 K

→ 6 CO 2(g) + 3H 2 O( g ) + 3273 kJ ∆ comb H 0 ( benzene ) = −3273
kJ
2 mol

Neutralization Enthalpy: ∆neutrH0 is the enthalpy change associated to the

neutralization reaction between acids and bases.
P =1 bar
H+ ( aq ) + OH (−aq ) 
T = 298 K 1M
→ H 2 O(l ) + 57.0 kJ ∆ neutr H 0 = −57.0
kJ
mol

Formation Enthalpy: ∆fH0 is the enthalpy change associated to the

formation of a compound from its constituent elements
1
∆ f H 0 ( H 2 O (l ) ) = −285.83
P =1 bar kJ
H 2( g ) + O 2( g ) 
T = 298 K
→ H 2 O(l ) + 285.83 kJ
2 mol
Mar-16 Chapter-9 20
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction
To obtain information about heats of reaction
indirectly, we use the Hess’s law: the enthalpy ∆H= ∆1HA+ ∆2HA
change for any process is independent of the
particular way the process is carried out. The
underlying concept here is that enthalpy is a ∆H= ∆1HB+ ∆2HB
state function.
desired

Initial ∆H Final
state state

∆1HA Intermediate ∆2HA

State A

∆1HB Intermediate
∆2HB
State B
Mar-16 Chapter-9 21
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction
Enthalpy diagrams and the Hess’s Law have important practical implications.
The sum of the ∆H
for the different steps
along a cyclic
process is always CH4(g) + 2 O2(g)
null.
∆H2b=+519 kJ
CO(g) + ½ O2(g) + 2H2O(g)
∆H1=−802 kJ
For a particular set of ∆H2a =+283 kJ
reactants and
products, ∆H is the
same whether the CO2(g) + 2 H2O(g)
reaction takes place in
one step or in a series
of steps. ∆H1= −∆H2a −∆H2b
Mar-16 Chapter-9 22
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction
• Use the following thermochemical equations as needed to find the
heat of formation of diamond:
C(diamond) + O2(g) → CO2(g) ∆H° = –395.4 kJ
2 CO2(g) → 2 CO(g) + O2(g) ∆H° = 566.0 kJ
C(graphite) + O2(g) → CO2(g) ∆H° = –393.5 kJ
2 CO(g) → C(graphite) + CO2(g) ∆H° = –172.5 kJ

Mar-16 Chapter-9 23
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction
Hess’s law allows us to use tabulated ∆fH0 to calculate the enthalpy change
for virtually any chemical reaction. Formally, first the reactants are
converted to elements in their standard states, and then those elements
recombine to form the products.

Reactants Products
reactants ∆rH products

∑ ν j A( j) ∑ ν i A (i )
j Chemical reaction i

Formal ∆1H Elements in ∆2H Formal

step 2
step 1
standard state

products reactants
Exact ∆r H =
0
∑ ν i ∆ f H (i ) −
0
∑ ν j ∆f H 0 ( j )
calculations i j

νi, νj = stoichiometric coefficients

Mar-16 Chapter-9 24
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction

Standard enthalpies of formation ∆fH0

Substance ∆fH0 Substance ∆fH0 Substance ∆Hf0
kJ/mol kJ/mol kJ/mol
O2(g) 0 C(grafito) 0 C6H6(l) 49.0
O3(g) 142.3 C(diamante) 1.88 C2H5OH(l) −277.7
H2O(g) −241.82 CO(g) −110.5 NaCl(s) −410.9
H2O(l) −285.83 CO2(g) −393.5 CaCl2(s) −795.8
Fe(s) 0 CH4(g) −74.8 CaCO3(s) −1207.1
Hg(l) 0 C2H6(g) −84.7 CH3COOH(l) −487.0
Hg(g) 60.83 C3H8(g) −103.85 C6H12O6(s) −1274.4
C4H10(g) −147.6

Non-molecular
∆ f H (elements ) = 0
0
substances

Mar-16 Chapter-9 25
Chemistry: for
Engineering Students Hess’s Law and Heats of Reaction
• From tabulated data, find the standard enthalpy of reaction for the
decomposition of 1 mol of acetic acid CH3COOH(l) into methane and
carbon dioxide.

• The standard enthalpy change for the decomposition reaction of lime

(CaCO3(s)) to give calcium oxide and carbon dioxide is 178.1 kJ per mole
of CaCO3(s). Use this value and data in the Table of standard formation
enthalpies to calculate the standard enthalpy of formation of CaO(s).
Chemistry: for
Engineering Students Energy and Stoichiometry
Thermochemical equation allows for a treatment of energy as a product for an
exothermic reaction, and in an endothermic reaction, energy can be thought of
as a reactant. Keep in mind that the value of ∆H in a thermochemical equation
corresponds to the reaction taking place exactly as written.

Mass Molar
mass
Thermochemical
equation
Energy
Moles of released
substance
Reac→Prod ∆H or absorbed
Molarity
Volume

Mar-16 Chapter-9 27
Chemistry: for
Engineering Students Energy and Stoichiometry
9.66 Sulfur trioxide can be removed from the exhaust gases of power plants
by reaction with lime according to the equation,
CaO(s) + SO3(g) → CaSO4(s), with ∆rH°= –886 kJ
If 240 kg of SO3 is to be removed, how much heat is released?

Mar-16 Chapter-9 28
Chemistry: for
Engineering Students
Problems and Exercises
9.2 What are the advantages of electricity as a type of energy that make it worth
generating despite the sizable losses that occur during this process?
9.10 The kinetic energy of molecules is often used to induce chemical reactions. The
bond energy in an O2 molecule is 8.22 × 10–19 J. Can an O2 molecule traveling at 780
m/s provide enough energy to break the O=O bond? What is the minimum velocity of an
O2 molecule that would give a kinetic energy capable of breaking the bond if it is
converted with 100% efficiency?
9.22 PV-work occurs when volume changes and pressure remains constant. If volume is
held constant, can PV-work be done? What happens to the expression of the First Law
of Thermodynamics when volume is held constant?
9.24 In which case is heat added to the system: (a) ∆E = –43 J, w = 40 J; or (b) ∆E = 31
J, w = 34 J?
9.26 Gas furnaces have achieved impressive efficiency levels largely through the
addition of a second heat exchanger that condenses water vapor that would otherwise
escape out the exhaust system attached to the furnace. How does this process improve
efficiency?
9.30 For the example of shallow water and sandy beaches, which material has a larger
heat capacity or specific heat? How does a hot day at the beach provide evidence for
your answer?
Mar-16 Chapter-9 29
Chemistry: for
Engineering Students
Problems and Exercises
9.35 A piece of titanium metal with a mass of 20.8 g is heated in boiling water to 99.5°C
and then dropped into a coffee cup calorimeter containing 75.0 g of water at 21.7°C.
When thermal equilibrium is reached, the final temperature is 24.3°C. Calculate the
specific heat capacity of titanium.
9.38 The energy densities of various types of coal are: anthracite 35 kJ/g; sub-
bituminous 31 kJ/g; bituminous 28 kJ/g; Lignite 26 kJ/g. An unknown sample of one of
these coals is burned in an apparatus with a calorimeter constant of 1.3 kJ/°C. When a
0.367-g sample is used, the temperature change is 8.75°C. Which type of coal is the
sample?
9.47 If 14.8 kJ of heat is given off when 1.6 g of HCl condenses from vapor to liquid,
what is ∆condH for this substance?
9.50 When a 13.0-g sample of NaOH(s) dissolves in 400.0 mL water in a coffee cup
calorimeter, the temperature of the water changes from 22.6°C to 30.7°C. Assuming that
the specific heat capacity of the solution is the same as for water, calculate (a) the heat
transfer from system to surroundings and (b) ∆H for the reaction NaOH(s)→Na+(aq)+OH–(aq)

9.52 Write the formation reaction for each of the following substances: (a) CH4(g), (b)
C3H8(ℓ), (c) HCl(g), (d) C6H12O6(s), (e) NaF(s).

Mar-16 Chapter-9 30
Chemistry: for
Engineering Students
Problems and Exercises
9.56 The phase change between graphite and diamond is difficult to observe directly.
Both substances can be burned, however. From these equations, calculate ∆H° for the
conversion of diamond into graphite.
C(s, graphite) + O2(g) → CO2(g) ∆H° = –393.51 kJ
C(s, diamond) + O2(g) → CO2(g) ∆H° = –395.94 kJ
9.63 For the reaction N2(g) + O2(g) → 2 NO(g), ∆H° = 180.5 kJ, how much energy is
needed to generate 35 moles of NO(g)?

9.67 Reactions of hydrocarbons are often studied in the petroleum industry. One such
reaction is 2 C3H8(g) → C6H6(ℓ) + 5 H2(g). If 35 L of propane at 25°C and 0.97 atm is to be
reacted, how much heat must be supplied at standard conditions?
9. 85 You want to heat the air in your house with natural gas (CH4). Assume your house
has 75 m2 of floor area and that the ceilings are 2.50 m from the floors. The air in the
house has a molar heat capacity of 29.1 J/mol/K. (The number of moles of air in the
house can be found by assuming that the average molar mass of air is 28.9 g/mol and
that the density of air at these temperatures is 1.22 g/L) What mass of methane do you
have to burn to heat the air from 15.0°C to 22.0°C?

Mar-16 Chapter-9 31
Chemistry: for
Engineering Students
Problems and Exercises
9.102 Suppose that there is 2.43 mol of nitrogen gas in an insulated, sealed 31.7-L
container initially at 285 K. If a 5.44-kg block of iron at 755 K is placed in this
container and it is sealed again (with no loss of nitrogen), what is the final pressure of
the nitrogen gas?

5.47 (TCS) Consider the combustion of liquid methanol,

CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(l) ∆H=−726.5 kJ
(a) What is the enthalpy change for the reverse reaction?(b) Balance the forward
reaction with whole-number coefficients. What is ∆H for the reaction represented by this
equation? (c) Which is more likely to be thermodynamically favored, the forward
reaction or the reverse reaction? (d) If the reaction were written to produce H2O(g)
instead of H2O(l), would you expect the magnitude of ∆H to increase, decrease, or stay
the same? Explain.

5.102 (TCS) Meals-ready-to-eat (MREs) are military meals that can be heated on a
flameless heater. The heat is produced by the following reaction:
Mg(s) + 2H2O(l) → Mg(OH)2(s) + H2(g)
(a) Calculate the standard enthalpy change for this reaction. (b) Calculate the number
of grams of Mg needed for this reaction to release enough energy to increase the
temperature of 75 mL of water from 21 °C to 79 °C.

Mar-16 Chapter-9 32