Chapter 3

ENERGY IN TRANSIT
Big Idea: Heat Flow in
Thermochemical Processes

Theme Focus: A
thermochemical process will
either absorb or release
energy in the form of heat.
 LEARNING OBJECTIVES

• Explain the energy changes during chemical

reactions
• Distinguish between exothermic and
endothermic processes
• Explain the First Law of Thermodynamics
• Explain the enthalpy of a reaction
• Write the thermochemical equation for a
chemical reaction
 LEARNING OBJECTIVES
• Calculate the change in enthalpy of a given
reaction using Hess’s Law
 Lesson 3.1

ENERGY CHANGES IN CHEMICAL

REACTIONS
ESSENTIAL QUESTION:

WHAT THERMOCHEMICAL PROCESSES ARE

OBSERVED EVERYDAY?
Thermochemistry is the study of energy or heat flow that
accompanies a chemical reaction and/or physical
transformations.

Heat is a form of energy transfer between two objects as a

result of their difference in temperature.

Temperature = Thermal Energy

Temperature is a measure of the thermal energy.

Energy generally flows from a

hotter object to a cooler one until
thermal equilibrium is reached
900C 400C
A chemical system and its surroundings

The system is the

the surroundings part of the universe
being studied

The surrounding
includes everything
else in the universe

the system
 HEAT (q)
Exothermic process (-q) is any process that gives off heat –
transfers thermal energy from the system to the surroundings.
H2O (g) H2O (l) + energy
Endothermic process (+q) is any process in which heat
has to be supplied to the system from the surroundings.
energy + H2O (s) H2O (l)
Reaction between water and metallic sodium

The reaction is exothermic.

The heat generated in the
process is enough to melt the
metal and ignite the gas.
 Exercise: Determine whether the following
processes are endothermic or exothermic

1. Photosynthesis
2. Respiration
3. Burning of coal
4. Neutralization between an acid and a base
5. Combustion of gasoline
6. Solid lead (II) chloride dissolves only in hot water
7. Heating causes sodium bicarbonate to decompose
 Lesson 3.2

FIRST LAW OF THERMODYNAMICS

ESSENTIAL QUESTION:

HOW DO HEAT AND WORK AFFECT A SYSTEM?

 THERMODYNAMICS
-- one branch of thermodynamics is THERMOCHEMISTRY
which deals with the interconversion of energy between
two forms: heat (q) and work (w).
The Law of Conservation of DEsystem + DEsurroundings = 0
Energy requires that the total
energy change in the system or
and the surrounding must be DEsystem = -DEsurroundings
zero

The First Law of Thermodynamics: DEsystem = q + w

-- the law implies that the net energy flow to or from any
system comes in the form of either work or heat
 The Sign Conventions* for q, w and DE
q + w = DE

+ + +

+ - depends on sizes of q and w

- + depends on sizes 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.
 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

 Sample Problem
A system gives off 225 J of heat to the surroundings while
performing 645 J of work. Calculate the total energy change,
DE, of the system and identify if the whole process is
endothermic or exothermic
PLAN: Define system and surroundings, assign signs to q and w and
calculate DE. The verbs used in the sentence describe the individual
process as endothermic (+) or exothermic (-).

SOLUTION:
q = - 225 J w = - 645 J

DE = q + w = -225 J + (-645 J) = -870 J

 Sample Problem
When gasoline burns in a car engine, the heat released causes the
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 (DE) in J, kJ,
and kcal.
PLAN: Define system and surroundings, assign signs to q and w and calculate
DE. The answer should be converted from J to kJ and then to kcal.

SOLUTION: q = - 325 J w = - 451 J

DE = q + w = -325 J + (-451 J) = -776 J

kJ kcal
-776 J = -0.776 kJ -0.776 kJ = -0.185 kcal
103J 4.184 kJ
 Practice Exercise 3.2 (page 60)
1. What is the work done by a system when it absorbs 47 J
and gain 12 J of energy?
2. How much heat is released by a system when 45 J of
work is done on it to decrease its energy to 23 J?
Find DE when:

a.) 175J of work is done on a system that

evolves 50J of heat to the surroundings

b.) a gas absorbs 28kJ of heat and has

13kJ of work done on it
 Lesson 3.3

CALORIMETRY

ESSENTIAL QUESTION:

HOW IS HEAT RELATED TO CHANGES IN

TEMPERATURE?
 CALORIMETRY
-- involves the measurement of the quantity of heat
exchanged between a system and its surroundings.
The amount of heat absorbed or released by the system
is a function of its change in temperature:

q = CDT

C (capital letter) = heat capacity, the amount of energy

needed to increase the temperature of a substance by
1OC (in J/OC)
 SPECIFIC HEAT CAPACITY (c)
For a pure substance, C = mc where m is mass, and c is
specific heat

Therefore, q = mcDT

The specific heat (c) of a

substance is the amount of heat
(q) required to raise the
temperature of one gram of the
substance by 1OC.
 Table 3-1 Specific Heat of select substances
Substance Specific Heat Substance Specific Heat
Capacity (J/g∙OC ) Capacity (J/g∙OC )

Elements Solid 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
gold, Au 0.129 steel 0.45
Compounds

water, H2O(l) 4.184

ethyl alcohol, C2H5OH(l) 2.46
ethylene glycol, (CH2OH)2(l) 2.42
carbon tetrachloride, CCl4(l) 0.862
 CALORIMETER
-- an insulator device used to experimentally determine
the heat capacity of a substance
A calorimeter assembly
The system is assumed to
exchange heat only with the
water (surrounding), which is
expressed as:

qsys = - qsurr
qsys = - qwater
qsys = - (mcDt) water
 COFFEE CUP CALORIMETER

-- a typical calorimeter
used in experimentation
which is usually made of
a polystyrene cup

A coffee cup calorimeter

 Sample 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 250C to 300.0C? The specific
heat capacity (c) of Cu is 0.387 J/g∙ 0C.

PLAN: Given the mass, specific heat capacity and change in

temperature, we can use q = c x mass x DT to find the answer.

SOLUTION: 0.387 J
q= 0
x 125 g x (300-25)0C = 1.33x104 J
g∙ C
 Sample Problem

How much heat is given off when

an 869 g iron bar cools from 940C
to 5.00C? c of Fe = 0.444 J/g • 0C

SOLUTION:

Dt = tfinal – tinitial = 50C – 940C = -890C

q = mcDt = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

 Sample Problem
You heat 22.05 g of a solid in a test tube to 100.000C and
add it to 50.00 g of water in a coffee-cup calorimeter. The
water temperature changes from 25.100C to 28.490C. Find
the specific heat capacity of the solid.

PLAN: Find the temp changes of the water and of the solid by using Tfinal
– Tinitial. Set the heat released by the solid (-qsolid) equal to heat
absorbed by the water (qwater). c of water is known.

SOLUTION:
DTwater = 28.490C - 25.100C = 3.390C

DTsolid = 28.490C - 100.000C = -71.510C

Continued next slide
 Sample Problem
Continued…

Solving for csolid,

-qsolid = qwater

- msolidcsolidDTsolid = mwatecwateDTwater
mwatercwaterDTwater
csolid = -
msolidDTsolid
Substituting the values,

csolid = 0.450 J/g0C

 Practice Exercise
1. A 295 g aluminum engine part at an initial temperature of
13.000C absorbs 75.0 kJ of heat. What is the final
temperature of the part? c of Al = 0.900 J/g • 0C
2. An unknown mass of heated iron (initially at 500.0⁰C)
was quickly transferred to a calorimeter containing 240. g
of water (initially at 20.0oC). When thermal equilibrium is
reached, the system has a temperature of 42.0oC.
Calculate the mass of the iron. c of iron = 0.451 J/g oC.
 Lesson 3.4

ENTHALPY OF A CHEMICAL REACTION:

THERMOCHEMICAL EQUATIONS

ESSENTIAL QUESTION:

WHY DO WE MEASURE THE ENTHALPY OF A

CHEMICAL REACTION?
 THERMOCHEMICAL EQUATIONS
-- a chemical equations that show the value and direction
of heat involved in a reaction
Enthalpy (H) is a form of chemical energy used to quantify the
heat absorbed or released by a chemical reaction at constant
atmospheric pressure.
Enthalpy of a reaction (DH) is the difference between the
enthalpy of the products and enthalpy of the reactants

DH = H (products) – H (reactants)
+ DH = endothermic
- DH = exothermic
 THERMOCHEMICAL EQUATIONS
Example

CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l) DH = -890.4 kJ

When 1 mole of methane and 2 moles of

Meaning oxygen gas combust to form one mole of
carbon dioxide and two moles of liquid water,
890.4 kJ of heat is released.

Enthalpy is an extensive property. If the amount of reactants and

products in a thermochemical equation is multiplied by 2, the value of
enthalpy is also multiplied by 2. If multiplied by ½, then the value is
also reduced to half.
 ENTHALPIES UNDER STANDARD
CONDITIONS

Standard molar enthalpy of formation o

f (DH f) of a
compound is the change in enthalpy when 1 mole of the
compound is formed from its elements under standard
conditions (1 atm, 250C)

The standard enthalpy of formation of any element in its

most stable form is zero.
DH0f (O2) = 0 DH0f (C, graphite) = 0
DH0f (O3) = 142 kJ/mol DH0f (C, diamond) = 1.90 kJ/mol
 ENTHALPIES UNDER STANDARD
CONDITIONS
Standard enthalpy of reaction (DHorxn) is the enthalpy
of a reaction carried out at 1 atm.
aA + bB cC + dD

DH0rxn = [ cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]

DH0rxn = S DH0f (products) - S DH0f (reactants)

Table 3-2 Selected Standard Heats of Formation at 25oC (298K)

Formula DH0f (kJ/mol) Formula DH0f (kJ/mol) Formula DH0f (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) 0.3
Oxygen
HCN(g) 135 SO2(g) -296.8
O2(g) 0
CSs(l) 87.9
O3(g) 143 SO3(g) -396.0
Chlorine H2O(g) -241.8
Cl(g) 121.0 H2O(l) -285.8
 Sample Problem
Nitric acid, whose worldwide annual production is about 8
billion kilograms, is used to make many products, including
fertilizer, 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 DHorxn from DHof values.

PLAN: Look up the DHof values on Table 3-2

Continued next slide

 Sample Problem
Continued…

SOLUTION:

DHrxn = S DHof (products) - S DHof (reactants)

DHrxn = [4(DHof NO(g) + 6(DHof H2O(g)] - [4(DHof NH3(g) + 5(DHof 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)]

DHrxn = -906 kJ
 HESS’S LAW
-- if a reaction is an overall process that can be attained
through a series of steps of reactions, the enthalpy of this
overall reaction can be calculated using Hess’s Law: the
enthalpy of a sum of a series of reactions is equal to the
sum of the enthalpies of those two reactions.
RULES:
1. Enthalpy is an extensive property; it depends on the
amount of reactants and products.
2. The H for a forward reaction is equal in magnitude but
opposite in sign to its reverse reaction.
3. The H for a reaction is the same whether it occurs in
one step or in a series of steps.
 Sample Problem
Two gaseous pollutants that form in auto exhaust are
CO and NO. An environmental chemist is studying
ways to convert them to less harmful gases through the
following equation:

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

Given the following information, calculate the unknown DH:

Equation A: CO(g) + 1/2O2(g) CO2(g) DHA = -283.0 kJ
Equation B: N2(g) + O2(g) 2NO(g) DHB = 180.6 kJ

Continued next slide

 Sample Problem
Continued…

PLAN: Equations A and B have to be manipulated by reversal and/or

multiplication by factors in order to sum to the first, or target, equation.

SOLUTION: Multiply Equation B by 1/2 and reverse it.

CO(g) + 1/2O2(g) CO2(g) DHA = -283.0 kJ
NO(g) 1/2N2(g) + 1/2O2(g) ½ DHB = ½ (-180.6 kJ) = -90.3 kJ
CO(g) + NO(g) CO2(g) + 1/2N2(g) DHrxn = -373.3 kJ
 Sample Problem

Calculate the standard enthalpy of formation of CS2 (l)

given that:
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) DH0rxn = -296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DHrxn 0 = -1072 kJ

The enthalpy of formation reaction for CS2 is:

C(graphite) + 2S(rhombic) CS2 (l)

Continued next slide

 Sample Problem
Continued…

SOLUTION:

Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0rxn = -296.1x2 kJ
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DHrxn
0 = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

DH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
 Practice Exercise
1. Hydrazine (N2H4) is a fuel used by some spacecraft. It is normally
oxidized by N2O4 according to the equation:
N2H4 (l) + N2O4 (g)  2 N2O (g) + 2 H2O (g)
Calculate DHorxn for this reaction using standard enthalpies of formation.
DHof
N 2O 81.6 kJ
H 2O -241.8 kJ
N 2H 4 50.6 kJ
N 2 O4 9.16 kJ

2. Find DHrxn for the reaction: N2O (g) + NO2 (g)  3 NO (g)
Use the following reactions with known DH:
2 NO (g) + O2 (g)  2 NO2 (g) DH = -113.1 kJ
N2 (g) + O2 (g)  2 NO (g) DH = +182.6 kJ
2 N2O (g)  2 N2 (g) + O2 (g) DH = -163.2 kJ
 Seatwork
1. The highly exothermic thermite reaction, in which aluminum reduces
iron(III) oxide to elemental iron, has been used by railroad repair crews
to weld rails together.
2Al(s) + Fe2O3(s)  2Fe(s) + Al2O3(s), DH = -850 kJ
What mass of iron is formed when 725 kJ of heat are released?

2. Use Hess's Law to calculate the enthalpy change for the reaction
WO3(s) + 3H2(g)  W(s) + 3H2O(g) from the following data:

2W(s) + 3O2(g)  2WO3(s), DH = -1685.4 kJ

2H2(g) + O2(g)  2H2O(g), DH = -477.84 kJ

3. Calculate the DHrxn for the decomposition of calcium carbonate to

calcium oxide and carbon dioxide. DHf [CaCO3(s)] = -1206.9 kJ/mol;
DHf [CaO(s)] = -635.1 kJ/mol; DHf [CO2(g)] = -393.5 kJ/mol.
CaCO3(s)  CaO(s) + CO2(g)