Chapter 6

Thermochemistry: Energy Flow and Chemical Change

6-1
 Thermochemistry: Energy Flow and Chemical Change

6.1 Forms of Energy and Their Interconversion

6.2 Enthalpy: Heats of Reaction and Chemical Change

6.3 Calorimetry: Laboratory Measurement of Heats of Reaction

6.4 Stoichiometry of Thermochemical Equations

6.5 Hess’s Law of Heat Summation

6.6 Standard Heats of Reaction (Horxn)

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 Some Definitions
System: that part of the universe whose change we are going
to observe

Surroundings: everything else relevant to the change

INTERNAL ENERGY, E

Each particle in a system has potential and kinetic energy;

the sum of these energies for all particles in a system is
the internal energy, E.

In a chemical reaction: when reactants are converted to

products, E changes (E).

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 E = Efinal - Einitial = Eproducts - Ereactants

Energy diagrams for the transfer of internal energy (E)

between a system and its surroundings

Figure 6.2

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 E = q + w where q = heat and w = work

A system transferring energy as heat only

Figure 6.3
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 Sign Conventions

The numerical values of q and w can be either positive or negative,

depending on the change the system undergoes.

Energy coming into the system is positive; energy going out from the
system is negative.

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 A system losing energy as work only

Pressure-volume
work (PV work)

Figure 6.4
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 Table 6.1 Sign Conventions for q, w and E

q + w = E

+ + +

+ - depends on magnitudes of q
and w

- + depends on magnitudes of q
and w

- - -

For q: (+) means system gains heat, (-) means system loses heat.

For w: (+) means work done on system, (-) means work done by system.
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 Law of Conservation of Energy
(First Law of Thermodynamics)

Euniverse = Esystem + Esurroundings = 0

Units of Energy

joule (J) 1 J = 1 kg m2/s2

calorie (cal) 1 cal = 4.184 J

British Thermal Unit 1 Btu = 1055 J

6-9
 Some quantities of energy

Figure 6.5

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 Sample Problem 6.1 Determining the Change in Internal Energy E of
a System

PROBLEM: When gasoline burns in a car engine, the heat released causes
the combustion products, CO2 and H2O, to expand, which
pushes the pistons outward. Excess heat is removed by the
car’s cooling system. If the expanding gases do 451 J of work
on the pistons and the system loses 325 J to the surroundings
as heat, calculate the change in energy (E) in J, kJ, and kcal.

PLAN: Define the system and the surroundings, assign signs to q and w, and
calculate E. The answer in units of J is converted to kJ and to kcal.

SOLUTION: q = (-) 325 J (system loses heat) w = (-) 451 J (system does work)

E = q + w = -325 J + (-451 J) = -776 J

kJ kcal
-776 J x = -0.776 kJ -0.776 kJ x = -0.185 kcal
103J 4.184 kJ

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 E is a state function - depends on current state of the system,
not on the path taken to reach that state.

q and w are not state functions but E is path independent

Two different paths for the energy change of a system

Figure 6.6
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 Pressure-volume
work

In this case, the system

does PV work on the
surroundings; thus w is
negative in sign.

Figure 6.7
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 For reactions that occur at constant pressure….

The Definition of Enthalpy

H ≈ E for:
w = - PV 1. Reactions that do not involve gases.

2. Reactions in which the number of

H = E + PV moles of gas does not change.

3. Reactions in which the number of

moles of gas changes but
qp = E + PV = H q is >>> PV.

H is a state function.
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 Enthalpy diagrams for exothermic and endothermic processes

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

heat + H2O(s) H2O(l)

Heat is released; Heat is absorbed;

enthalpy decreases. enthalpy increases.

Figure 6.8
6-15
 Sample Problem 6.2 Drawing Enthalpy Diagrams and Determining
the Sign of H
PROBLEM: In each of the following cases, determine the sign of H, state
whether the reaction is exothermic or endothermic, and draw an
enthalpy diagram.
(a) H2(g) + 1/2O2(g) H2O(l) + 285.8 kJ

(b) 40.7 kJ + H2O(l) H2O(g)

PLAN: Determine whether heat is a reactant or a product. As a reactant,

the products are at a higher energy and the reaction is
endothermic. The opposite is true for an exothermic reaction.
SOLUTION:
(a) The reaction is exothermic. (b) The reaction is endothermic.

H2(g) + 1/2O2(g) (reactants) H2O(g) (products)

EXOTHERMIC H = -285.8 kJ ENDOTHERMIC H = +40.7 kJ

H2O(l) (products) H2O(l) (reactants)

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 Some Important Types of Enthalpy Change

heat of combustion (Hcomb)

1C4H10(l) + 13/2O2(g) 4CO2(g) + 5H2O(g)

heat of formation (Hf)

K(s) + 1/2Br2(l) 1KBr(s)

Standard quantity
heat of fusion (Hfus) of either reactant
or product: 1 mol
1NaCl(s) NaCl(l)

heat of vaporization (Hvap)

1C6H6(l) C6H6(g)

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 Components of Internal Energy

Contributions to the kinetic energy:

• The molecule moving through space, Ek(translation)

• The molecule rotating, Ek(rotation)

• The bound atoms vibrating, Ek(vibration)

• The electrons moving within each atom, Ek(electron)

Contributions to the potential energy:

• Forces between the bound atoms vibrating, Ep(vibration)

• Forces between nucleus and electrons and between electrons in each

atom, Ep(atom)

• Forces between the protons and neutrons in each nucleus, Ep(nuclei)

• Forces between nuclei and shared electron pair in each bond, Ep(bond)

6-18
 Figure 6.9

Components of internal
energy (E)

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 H2(g) + F2(g) 2HF(g) + 546 kJ (exothermic)

Bonds absorb energy when they break and release energy when they form.

Weaker bonds = easier to break = higher in energy (less stable, more reactive)

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 Where does the heat of reaction come from?

The energy released or absorbed during a chemical reaction

is due to differences between the strengths of reactant bonds
and product bonds.

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 Table 6.2 Heats of Combustion (Hcomb) of Some Carbon Compounds

Two-Carbon Compounds One-Carbon Compounds

Ethane (C2H6) Ethanol (C2H6O) Methane (CH4) Methanol (CH4O)

H H H H H H
structural H C C H H C C O H H C H H C O H
formulas
H H H H H H

sum of C-C and

7 6 4 3
C-H bonds

sum of C-O and

0 2 0 2
O-H bonds

Hcomb(kJ/mol) -1560 -1367 -890 -727

Hcomb(kJ/g) -51.88 -29.67 -55.5 -22.7

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 Table 6.3 Heats of Combustion of Some Fats and Carbohydrates

Substance Hcomb(kJ/g)
Fats
vegetable oil -37.0
margarine -30.1

butter -30.0

Carbohydrates
table sugar (sucrose) -16.2

brown rice -14.9

maple syrup -10.4

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 Ball-and-stick molecular models of a carbohydrate
(sucrose) and a triglyceride (triolean)

A more “oxidized” fuel A more “reduced” fuel

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 Calorimetry = laboratory measurement of heats of reaction

heat capacity = an object’s capacity to absorb heat = the quantity

of heat required to change its temperature by 1 K

q = constant x T (the constant of proportionality is equal

to the heat capacity; in units of J/K)

specific heat capacity (c) = the quantity of heat required to change

the temperature of 1 gram of a substance by 1 K (in units of J/g.K)

q = c x mass x T

molar heat capacity (C) = the quantity of heat required to change

the temperature of 1 mole of a substance by 1 K (in units of J/mol.K)

6-25
 Table 6.4 Specific Heat Capacities of Some Elements,
Compounds and Materials

Substance Specific Heat Substance Specific Heat

Capacity (J/g*K) Capacity (J/g*K)

Elements Materials
aluminum (Al) 0.900 wood 1.76
graphite (C) 0.711 cement 0.88
iron (Fe) 0.450 glass 0.84
copper (Cu) 0.387 granite 0.79
steel 0.45
gold (Au) 0.129
Compounds

water, H2O(l) 4.184

ethyl alcohol, C2H5OH(l) 2.46
ethylene glycol, (CH2OH)2(l) 2.42
carbon tetrachloride, CCl4(l) 0.864

6-26
 Sample Problem 6.3 Calculating the Quantity of Heat from the
Specific Heat Capacity

PROBLEM: A layer of copper welded to the bottom of a skillet weighs 125 g.

How much heat is needed to raise the temperature of the copper
layer from 25 oC to 300. oC? The specific heat capacity (c) of
Cu is 0.387 J/g.K.
PLAN: Given the mass, specific heat capacity and change in temperature, we
can use q = c x mass x T to find the answer. T in oC and K are the
same.

SOLUTION: 0.387 J
q= x 125 g x (300-25)oC = 1.33 x 104 J
g.K

6-27
 Calorimeter. A device
used to measure the
heat released or absorbed
by a physical or chemical
process.

A coffee-cup
calorimeter
(constant P)

-qsolid = qwater

Figure 6.10
6-28
 Sample Problem 6.4 Determining the Specific Heat Capacity of a
Solid
PROBLEM: A 25.64 g sample of a solid was heated in a test tube to 100.00 oC
in boiling water and carefully added to a coffee-cup calorimeter
containing 50.00 g of water. The water temperature increased from
25.10 oC to 28.49 oC. What is the specific heat capacity of the
solid? (Assume all the heat is gained by the water)
PLAN: It is helpful to use a table to summarize the data given. Then work the
problem realizing that heat lost by the system must be equal to that
gained by the surroundings.
mass (g) c (J/g.K) Tinitial Tfinal T

solid 25.64 ? 100.00 28.49 -71.51

H2O 50.00 4.184 25.10 28.49 3.39
SOLUTION:
25.64 g x c x -71.51 K = - 50.00 g x 4.184 J/g.K x 3.39 K
csolid = - 50.00 g x 4.184 J/g.K x 3.39 K
= 0.387 J/g.K
25.64 g x -71.51 K

6-29
 Calorimetry at
Constant Volume

A bomb calorimeter:
used to measure qv

Figure 6.11

6-30
 Sample Problem 6.5 Calculating the Heat of Combustion

PROBLEM: A manufacturer claims that its new diet dessert has “fewer than
10 Calories (10 kcal) per serving”. To test the claim, a chemist
at the Department of Consumer Affairs places one serving in a
bomb calorimeter and burns it in O2 (the heat capacity of the
calorimeter = 8.151 kJ/K). The temperature increases by 4.937
o
C. Is the manufacturer’s claim correct?
PLAN: - qsample = qcalorimeter

SOLUTION: qcalorimeter = heat capacity x T

= 8.151 kJ/K x 4.937 K

= 40.24 kJ

40.24 kJ x kcal = 9.62 kcal < 10 Calories = 10 kcal

4.184 kJ

The manufacturer’s claim is correct.

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 Summary of the relationship between
amount (mol) of substance and the heat
AMOUNT (mol) (kJ) transferred during a reaction
of compound A

AMOUNT (mol)
of compound B
molar ratio from
balanced equation

HEAT (kJ)
Hrxn (kJ/mol) gained or lost

Figure 6.12
6-32
 Sample Problem 6.6 Using the Heat of Reaction (Hrxn) to Find
Amounts
PROBLEM: The major source of aluminum in the world is bauxite (mostly
aluminum oxide). Its thermal decomposition can be represented by:
Al2O3(s) 2Al(s) + 3/2O2(g) Hrxn = 1676 kJ
If aluminum is produced this way, how many grams of aluminum can
form when 1.000 x 103 kJ of heat is transferred?

PLAN: SOLUTION:
2 mol Al 26.98 g Al
heat (kJ) 1.000 x 103 kJ x x
1676 kJ 1 mol Al
1676 kJ = 2 mol Al
= 32.20 g Al
mol of Al

x M (g/mol)

g of Al

6-33
 Hess’s Law of Heat Summation

The enthalpy change of an overall process is the sum of

the enthalpy changes of its individual steps.

Used to predict the enthalpy change (a) of an overall reaction

that cannot be studied directly, and/or (b) of an overall reaction
that can be separated into distinct reactions whose enthalpy
changes can be measured individually.

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 Sample Problem 6.7 Using Hess’s Law to Calculate an Unknown H

PROBLEM: Two gaseous pollutants that form auto exhaust are CO and NO.
An environmental chemist is studying ways to convert them into
less harmful gases through the following equation:

CO(g) + NO(g) CO2(g) + 1/2N2(g) H = ?

Given the following information, calculate the unknown H.

Equation A: CO(g) + 1/2O2(g) CO2(g) HA = -283.0 kJ

Equation B: N2(g) + O2(g) 2NO(g) HB = +180.6 kJ

PLAN: Equations A and B have to be manipulated by reversal and/or multiplied
by factors in order to sum to the target equation.
SOLUTION: Multiply Equation B by 1/2 and reverse it.

CO(g) + 1/2O2(g) CO2(g) HA = -283.0 kJ

NO(g) 1/2N2(g) + 1/2O2(g) HB = -90.3 kJ

CO(g) + NO(g) CO2(g) + 1/2N2(g) Hrxn = -373.3 kJ

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 Specifying Standard States

For a gas, the standard state is 1 atm; ideal gas behavior is

assumed.

For a substance in aqueous solution, the standard state is

1 M concentration (1 mol/liter solution).

For a pure substance (element or compound), the standard

state is usually the most stable form of the substance at 1
atm and the temperature of interest (usually 25 oC (298 K).

Horxn = standard heat of reaction

(enthalpy change determined with all

substances in their standard states)

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 Formation Equations

In a formation equation, 1 mol of a compound forms from its

elements. The standard heat of formation (Hof) is the enthalpy
change for the formation equation when all substances are
in their standard states.

C(graphite) + 2H2(g) CH4(g) Hof = -74.9 kJ

An element in its standard state is assigned a Hof of 0.

Most compounds have a negative Hof (i.e., the compound

is more stable than its component elements).

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 Table 6.5 Selected Standard Heats of Formation at 25 oC (298 K)

Formula Hof (kJ/mol) Formula Hof (kJ/mol) Formula Hof (kJ/mol)

calcium silver
Cl2(g) 0
Ca(s) 0 Ag(s) 0
HCl(g) -92.3
CaO(s) -635.1 AgCl(s) -127.0
CaCO3(s) -1206.9 hydrogen
H(g) 218 sodium
carbon
H2(g) 0 Na(s) 0
C(graphite) 0
C(diamond) 1.9 nitrogen Na(g) 107.8
CO(g) -110.5 N2(g) 0 NaCl(s) -411.1
CO2(g) -393.5 NH3(g) -45.9 sulfur
CH4(g) -74.9 NO(g) 90.3 S8(rhombic) 0
CH3OH(l) -238.6 S8(monoclinic) 2
oxygen
HCN(g) 135 SO2(g) -296.8
O2(g) 0
CS2(l) 87.9
O3(g) 143 SO3(g) -396.0
chlorine H2O(g) -241.8
Cl(g) 121.0 H2O(l) -285.8
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 Sample Problem 6.8 Writing Formation Equations

PROBLEM: Write balanced equations for the formation of 1 mol of the following
compounds from their elements in their standard states and include
Hof.
(a) Silver chloride, AgCl, a solid at standard conditions.
(b) Calcium carbonate, CaCO3, a solid at standard conditions.
(c) Hydrogen cyanide, HCN, a gas at standard conditions.

PLAN: Use the table of heats of formation (Table 6.5) to calculate Hof
values.
SOLUTION:

(a) Ag(s) + 1/2Cl2(g) AgCl(s) Hof = -127.0 kJ

(b) Ca(s) + C(graphite) + 3/2O2(g) CaCO3(s) Hof = -1206.9 kJ

(c) 1/2H2(g) + C(graphite) + 1/2N2(g) HCN(g) Hof = 135 kJ

6-39
 The general process for determining Horxn from Hof values

Figure 6.13

6-40
 Sample Problem 6.9 Calculating the Standard Heat of Reaction from
Standard Heats of Formation
PROBLEM: Nitric acid, whose worldwide annual production is about 8 billion kg,
is used to make many products, including fertilizers, dyes and
explosives. The first step in the industrial production process is the
oxidation of ammonia:
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

Calculate Horxn from Hof values.

PLAN: Look up Hof values (Table 6.5) and use Hess’s Law to find
Horxn.
SOLUTION: Horxn =  mHof (products) -  nHof (reactants)

Horxn = [4Hof NO(g) + 6Hof H2O(g)] - [4Hof NH3(g) + 5Hof O2(g)]

= [(4 mol)(90.3 kJ/mol) + (6 mol)(-241.8 kJ/mol)] -

[(4 mol)(-45.9 kJ/mol) + (5 mol)(0 kJ/mol)]

Horxn = -906 kJ
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