Thermochemistry

Chem B Jan 2010 - Ms. Jessvin Sidhu 1

Introduction

In general, all chemical reactions and chemical
processes involves energy change :-

Heat energy absorbed from the environment into
system = temp of environment/surrounding to ↓

Heat energy released from the system into the
environment to = temp of environment
/surrounding to ↑

WHY ???

Chem B Jan 2010 - Ms. Jessvin Sidhu 2

Enthalpy => Heat of Reaction

Chem B Jan 2010 - Ms. Jessvin Sidhu 3


http://www.mhhe.com/physsci/chemistry/a
nimations/chang_7e_esp/enm1s3_4.swf

Chem B Jan 2010 - Ms. Jessvin Sidhu 4

Introduction

A certain amount of chemical energy is stored
within every atom, molecule or ion.

This energy is the sum of the potential energy

(stored energy) + kinetic energy ( energy associated with
movement) of the substance and results from:
 The attraction & repulsion btwn protons and electrons
 The motion of the electrons
 The movement of the atoms.

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Enthalpy

The total energy stored in a substance is called
the enthalpy or heat content, of the substance.

Symbol for enthalpy is H (unit is Joule)

The First Law of Thermodynamics states that:-
 energy is neither created nor destroyed, but simply
changes from one form into another.
 Whenever energy is converted from one form into
another, the total quantity of energy remains the
same.

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Enthalpy

In all chemical reactions, the enthalpy/ energy of
the reactants and products differ (one is higher
than the other).

Unfortunately, we cannot directly measure the
heat content of a substance.

However, we can measure the change in
enthalpy when a substance undergoes a
chemical reaction.

??? = measuring the rise @ fall of temperature
of the surrounding.

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Exothermic Reactions

Chemical reactions that release heat to
the environment = temp ↑

In your opinion, which is higher ? Hreactant
or Hproducts ? (think First Law of Thermodynamics /
conservation of energy )

Chem B Jan 2010 - Ms. Jessvin Sidhu 8

Exothermic Reaction

The total chemical energy of the
reactants is more than the
energy of the products.

Since energy is never lost, the
difference in chemical energy
between the reactants and
products is released into the
environment = as heat energy.

Products are at lower energy level.
Hence products are more stable.

Chemical bonds in products are
stronger.
• The change in enthalpy during a reaction is known as the heat of
reaction and is denoted by ∆H

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Endothermic reaction

The chemical energy of the
reactant is less than the
energy of the reactants.

Energy must be absorbed from
the environment around the
reactants for the reaction to
occur.

Temperature of the
surrounding become lower.

Reactants are at lower energy
level. Hence reactants are
more stable.

Chemical bonds in reactants
are stronger.
Chem B Jan 2010 - Ms. Jessvin Sidhu 10
Standard Laboratory Conditions

The enthalpy change of reaction depends on the amount
of reactants used and the temperature of the reactants
compared to the products.

To remove those variables in enthalpy studies, the

following conditions are assumed:

This conditions are referred to as standard laboratory

conditions (SLC)
 Temperature at 25°C
 1 mole of substance is involved
 Concentration of solution is 1 mol/L ( 1M)
 Pressure is kept at 1 atm
 Heat change is measured in kilojoules (kJ)
Chem B Jan 2010 - Ms. Jessvin Sidhu 11
Thermochemical equations

Thermochemical equations are just like other balanced equations
except they also specify the heat absorbed or produced for the
reaction.

The heat flow is listed to the right of the equation using the symbol
∆H. The most common units are kJ/mol.

For example:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ∆H = -802 kJ/mol

Coefficients refer to the number of moles. Thus, the equation is read

as, when 1 mole of methane gas reacts with 2 moles of oxygen gas,
1 mole of carbon dioxide and 2 moles of water vapour forms and
802 kJ of energy is released.

∆H refers to the equation as it is written, even though the unit is

expressed as kJ/mol.

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Certain laws or rules apply when using
thermochemical equations:

∆H is directly proportional to the quantity of a substance that

reacts or is produced by a reaction.

Amount of energy produced is directly proportional to mass.

Therefore, if you double the coefficients in an equation, then the
value of ∆H is multiplied by two. For example:

C2H4 (g) + 3O2 (g)  2CO2 + 2H2O (l); ∆H θ = -1411 kJmol-1

2C2H4 (g) + 6O2 (g)  4CO2 + 4H2O (l); ∆H θ = -2822 kJmol-1

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∆H for a reaction is equal in magnitude but opposite
in sign to ∆H for the reverse reaction.

For example:

2H2 (g) + O2 (g)  2H2O (g) ∆H= - 468 kJ/mol

2H2O (g)  2H2 (g) + O2 (g) ∆H= + 468 kJ/mol

If a reaction is reversed, ∆H is equal to, but opposite in

sign, to that of the forward reaction.

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The physical state of matter must be shown, since
changes of state require energy changes:

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Sample problem

Sodium nitrate dissolves readily in water according to the equation

NaNO3(s) → NaNO3(aq); ∆H = +21.0 kJ mol–1

a Determine the energy change when 1.0 g of solid NaNO3 is

dissolved in water.

b Would you expect the temperature to rise or fall when sodium
nitrate dissolves in water? Explain your answer.

Chem B Jan 2010 - Ms. Jessvin Sidhu 16

 1

n(NaNO3) = =0.0117 mole
85
1 mole NaNO3 absorbs 21 kJ energy
0.0117 mole absorbs 0.0117 × 21 kJ = 0.25 kJ

The temperature will fall. Since the reaction is endothermic the

enthalpy of reactants is higher than the enthalpy of products, i.e. the
reaction absorbs energy.

Chem B Jan 2010 - Ms. Jessvin Sidhu 17


Calculate the energy released when the following
quantities of ethane gas burn according to the equation:

2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l); ∆H = –3120 kJ mol–1

a 3.00 mol

b 100 g

c 10.0 L at SLC

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m
M

From the equation, use stoichiometry to find energy

released.

2 mol C2H6 releases 3120 kJ of energy

3120

3.00 mol C2H6 releases 2 × 3.00 kJ

So energy = 4680 kJ

= 4.68 × 103 kJ

Chem B Jan 2010 - Ms. Jessvin Sidhu 19


Calculate the amount of ethane, using n = m
M

n(C2H6) =
100 g
30.068 g mol −1
= 3.326 mol

Use stoichiometry to find energy released.

2 mol C2H6 releases 3120 kJ of energy
3.326 mol C2H6 releases 3120 × 3.326 kJ
2
So energy released = 5189 kJ
= 5.19 × 103 kJ

Chem B Jan 2010 - Ms. Jessvin Sidhu 20


Calculate the amount of ethane, using n = V at SLC.
Vm
n(C2H6) = 10.0 L
24.5 L mol −1
= 0.4082 mol

Use stoichiometry to find energy released.

2 mol C2H6 releases 3120 kJ of energy

0.4082 mol C2H6 releases 3120 × 0.4082 kJ
2
So energy released = 636.7 kJ
= 637 kJ

Chem B Jan 2010 - Ms. Jessvin Sidhu 21

Practice

Calculate the energy released when the following
quantities of hydrogen gas burn according to the
equation:

2H2(g) + O2(g) →2H2O(g); ∆H = –572 kJ mol–1

a 1.00 mol

b 1.00 kg

c 100 L at SLC

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Sample problem:

What volume of hydrogen, measured at STP, must be burnt
according to the equation
2H2(g) + O2(g) →2H2O(g); ∆H = –572 kJ mol–1
in order to yield 100 kJ of heat energy?

Use stoichiometry to find the amount of H2.

572 kJ is released by 2 mol
100 kJ is released by 2 × 100 mol
n(H2) = 0.3497 mol 572

V
Calculate the volume of H2 at STP, using n = V
m
V(H2) = n × Vm
= 0.3497 mol × 22.4 L mol–1
= 7.83 LChem B Jan 2010 - Ms. Jessvin Sidhu 23

Butane is used as the fuel in pocket cigarette lighters. It is a liquid
when stored under pressure in the lighter, but vaporises when the
valve is opened. Combustion of butane is represented by the
equation:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l); ∆H = –5772 kJ mol–1

a How much energy is evolved when 10.0 g of butane burns

completely?

b How much energy is evolved when 0.100 L of butane,

measured at SLC, burns completely?

c Calculate the volume of butane, measured at 15°C and 108

kPa, that must be burnt to yield 1.00 kJ of energy. (Hint: PV = nRT)

Ans: 497 kJ, 11.8 kJ, 7.68 mL

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Answer

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Measuring enthalpy change- Calorimetry

The value of ∆H can be determined

experimentally by measuring the heat flow
accompanying a reaction at SLC.

The measurement of heat flow is

calorimetry; a device used to measure
heat flow is a calorimeter.

Chem B Jan 2010 - Ms. Jessvin Sidhu 26

Coffee-cup calorimeter

For solution of soluble salts.

The reactants and products of the rxn are the
system.

The water in which they dissolve as well as
the calorimeter are part of the surroundings.

We assume that calorimeter perfectly
prevents the gain or loss of heat from the
solution.

The heat produced by the reaction is entirely
absorbed by the solution; it does not escape
the calorimeter.

Heat lost by rxn = Heat gained by the soln
opposite occurs for endothermic rxn

We also assume that the calorimeter itself
doesn’t absorb heat ~~ low thermal conductivity

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Coffee-cup calorimeter

The heat energy gained or
lost by the soln. (water) can
be readily calculated from:
 Mass of the water
 Heat capacity of the solution
(cH2O = 4.18 J g-1 °C-1)
 Temperature change

Q = m x c x ∆T

Joule (J) J Tf – Ti
g
g. °C °C
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Sample problem

Suppose 200mL of boiling water is needed to make a
cup of tea. Calculate the energy required for a ‘teh-tarik’
if the initial water temperature is 18.0°C (density of water
is 1g/cm3 )

Ans:

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Sample problem

100mL of 1.0M HCl at 21.0°C and 100mL of 1.0 M NaOH at
22.0°C are mixed in a coffee cup calorimeter. The highest
temperature of the mixture is recorded to be 45.0°C. Calculate the
heat change (q) experienced during the reaction and the enthalpy
of neutralization for the reaction. (cH2O = 4.18 Jg-1K-1)

Although the usual name for ∆H is heat of reaction, there are

some reactions for which specific names have been given.
 Heat of solution is the change in enthalpy when 1 mole of any
substance dissolves in water.
 Heat of neutralisation is the change in enthalpy when an acid reacts
with a base to form 1 mole of water – exothermic.
 Heat of combustion is the change when 1 mole of substance burns
in air, and is always exothermic.

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Sample problem

50mL of 1.0M HCl at 21.0°C and 50mL of 1.0 M NaOH at 22.0°C
are mixed in a coffee cup calorimeter. The highest temperature of
the mixture is recorded to be 28.0°C. Calculate the heat change
(q) experienced during the reaction and the enthalpy of
neutralization for the reaction in kJ/mol. (cH2O = 4.18 J g-1 °C-1)

Ans: -54
Chem B Jan 2010 - Ms. Jessvin Sidhu 31
Practice question
When 50.0mL of 0.100M AgNO3 and 50.0mL of 0.100M HCl are
mixed in a constant-pressure calorimeter, the temperature of the
mixture increses from 22.20°C to 23.11°C. Calculate the ∆H for this
reaction in kJ/mol (cH2O = 4.18 J g-1 °C-1).

Ans: -68

Chem B Jan 2010 - Ms. Jessvin Sidhu 32

Homework
 Butane gas burns in oxygen producing carbon dioxide and steam
at 100°C as shown in the following equation.
 2C4H10 (g) + 13O2 (g)  8CO2 (g) + 10H2O (g) ∆H = -5728
kJ/mol . When the reaction product is returned to SLC (25°C) the
∆H has a value of -6168 kJ/mol.
 Explain the difference in the ∆H values obtained.

Chem B Jan 2010 - Ms. Jessvin Sidhu 33