THERMOCHEMISTRY

Objectives
1. Explain the energy changes during chemical
reactions.
2. Distinguish between endothermic and
exothermic processes.
3. Explain the First Law of Thermodynamics.
4. Explain enthalpy of a reaction.
5. Write the thermochemical equation for a
chemical reaction.
6. Calculate the change in enthalpy of a given
reaction using Hess Law.
Energy is the capacity to do work
Heat is the transfer of thermal energy between two
bodies that are at different temperatures.
Temperature is a measure of the thermal energy.
Thermal energy is the energy associated with the
random motion of atoms and molecules
Temperature = Thermal Energy

400C
900C greater thermal energy
Thermochemistry is the study of heat change in
chemical reactions.
The system is the specific SYSTEM SURROUNDINGS
part of the universe that is
of interest in the study.

open closed isolated

Exchange: mass & energy energy nothing
Endothermic and exothermic reactions
Endothermic reactions get
cold, they take in heat.
Exothermic reactions get hot,
they give out heat.

Chemical reactions take

place in two stages:
1. An endothermic bond breaking stage.
2. An exothermic bond making stage.
Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the
surroundings.
2H2 (g) + O2 (g) 2H2O (l) + energy
H2O (g) H2O (l) + energy
Endothermic process is any process in which heat has
to be supplied to the system from the surroundings.
energy + 2HgO (s) 2Hg (l) + O2 (g)
energy + H2O (s) H2O (l)
 Energy Level Diagram for an
Exothermic Reaction
Reactants have more
reactants chemical energy.
Energy / kJ)

Some of this is lost as

H=negative heat which spreads out
into the room.
products
Products now have
Progress of reaction (time) less chemical energy
than reactants.
© Boardworks Ltd 2003
 Energy Level Diagram for an
Endothermic Process
This is how much
products energy is taken in
Energy / kJ)

H=positive This is positive

because the
reactants products have
more energy than
Progress of reaction the reactants.
© Boardworks Ltd 2003
Examples of Exothermic Reactions
• Burning reactions including
the combustion of fuels.
• Detonation of explosives.
• Reaction of acids with
metals.
• Space shuttle on take off:
white clouds of water vapor
are formed
• Fireflies release energy in
the form of light
Examples of Endothermic
reactions
• Alka Seltzer and water…temperature goes
down.
• Photosynthesis
6CO2 + 6H2O + energy C6H12O6 + 6O2
First Law of Thermodynamics
• Also called the Conservation of Energy Law
• Energy can be changed from one form to
another, but it cannot be created or
destroyed. The total amount of energy and
matter in the Universe remains constant,
merely changing from one form to another.
• The sum of the heat transferred into the
system and the work done on the system
equals the change in the internal energy of
the system
Enthalpy (H) is used to quantify the heat flow into or out
of a system in a process that occurs at constant pressure.
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant
pressure

Hproducts > Hreactants

Hproducts < Hreactants

DH < 0 DH > 0
 Thermochemical Equations

Is DH negative or positive?

6.01 kJ are absorbed for every 1 mole of ice that melts at

00C and 1 atm.
H2O (s) H2O (l) DH = 6.01 kJ
 Thermochemical Equations

Is DH negative or positive?
System absorbs heat
Endothermic
DH > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at

00C and 1 atm.
H2O (s) H2O (l) DH = 6.01 kJ
 Thermochemical Equations

Is DH negative or positive?

890.4 kJ are released for every 1 mole of methane that is

combusted at 250C and 1 atm.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ
 Thermochemical Equations

Is DH negative or positive?
System gives off heat
Exothermic
DH < 0

890.4 kJ are released for every 1 mole of methane that is

combusted at 250C and 1 atm.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ
 Thermochemical Equations
• The stoichiometric coefficients always refer to the
number of moles of a substance
H2O (s) H2O (l) DH = 6.01 kJ
• If you reverse a reaction, the sign of DH changes
H2O (l) H2O (s) DH = -6.01 kJ
• If you multiply both sides of the equation by a factor n,
then DH must change by the same factor n.
2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ
6.3
 Thermochemical Equations
• The physical states of all reactants and products must
be specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ
H2O (l) H2O (g) DH = 44.0 kJ
How much heat is evolved when 266 g of white
phosphorus (P4) burn in air?
P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ
1 mol P4 -3013 kJ
266 g P4 x x 1 mol P = -6470 kJ
123.9 g P4
4
6.3
 Example
• What is the ∆H of the decomposition of 105.0g of
sodium bicarbonate to sodium carbonate, carbon
dioxide, and water.
2 NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) ∆H = +129 kJ

• Knowns: mNaHCO = 105.0 g

3

molesNaHCO = 84.01 g/mol

3

∆H = +129 kJ/2 mol NaHCO3

• Calculation:
105.0 g NaHCO3 1 mol NaHCO3 +129 kJ
1
×
84.01 g NaHCO3
×
2 mol NaHCO3 = 80.6 kJ
 Hess’s Law
• The heat evolved or absorbed in a chemical process is
the same whether the process takes place in one or
several steps.
• If two or more chemical equations can be added
together to produce an overall equation, the sum of
the enthalpy equals the enthalpy change of the
overall equation.
• This is called the Heat of Summation, ∆H
 Hess’s Law

Start
Finish
A State Function: Path independent.
Both lines accomplished the same
result, they went from start to finish.
Net result = same. 21
 Hess’s Law
Read through the whole question
Plan a Strategy
Evaluate the given equations.
Rearrange and manipulate the equations
so that they will produce the overall
equation.
Add the enthalpy terms.
Example 1
H2O(g) + C(s) → CO(g) + H2(g)
Use these equations to calculate the molar
enthalpy change which produces hydrogen
gas.
C(s) + ½ O2(g) → CO(g) ∆H = -110.5kJ
H2(g) + ½ O2(g) → H2O(g) ∆H = -241.8kJ
 H2O(g) + C(s) → CO(g) + H2(g)
Use these equations to calculate the
molar enthalpy change which producesRule 1:
hydrogen gas. ΔH for a reaction
is equal in
C(s) + ½ O2(g) → CO(g) ∆H = -110.5kJ
magnitude but
H2O(g) → H2(g) + ½ O2(g) ∆H = +241.8kJ
opposite in sign
to ΔH for the
____________________________________
reverse reaction
_
C(s) + H2O(g) → H2(g) + CO(g) ∆H=+131.3kJ
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy
change which produces butane gas.
C4H10(g) + 6 ½ O2(g) → 4CO2(g) + 5H2O(g) ∆H= -2657.4kJ/mol
C(s) + O2(g) → CO2(g) ∆H= -393.5kJ/mol
H2(g) + ½O2(g) → H2O(g) ∆H= -241.8kJ/mol
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy
change which produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
C(s) + O2(g) → CO2(g) ∆H= -393.5kJ/mol
H2(g) + ½O2(g) → H2O(g) ∆H= -241.8kJ/mol
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy
change which produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
4(C(s) + O2(g) → CO2(g)) ∆H= 4(-393.5kJ/mol)
H2(g) + ½O2(g) → H2O(g) ∆H= -241.8kJ/mol
Rule 2:
The magnitude of ΔH is directly proportional to the amount
of reactant or product
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy change which
produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
4C(s) + 4O2(g) → 4CO2(g) distribute the 4 ∆H= 4(-393.5kJ/mol)
H2(g) + ½O2(g) → H2O(g) ∆H= -241.8kJ/mol
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy change which
produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
4C(s) + 4O2(g) → 4CO2(g) distribute the 4 ∆H= 4(-393.5kJ/mol)
5(H2(g) + ½O2(g) → H2O(g)) distribute the 5 ∆H= 5(-241.8kJ/mol)
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy change which
produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
4C(s) + 4O2(g) → 4CO2(g) ∆H= 4(-393.5kJ/mol)
5H2(g) + 2½O2(g) → 5H2O(g) ∆H= 5(-241.8kJ/mol)
 Example 2
4C(s) + 5H2(g) → C4H10(g)
Use these equations to calculate the molar enthalpy
change which produces butane gas.
5H2O(g) + 4CO2(g) → 6 ½ O2(g) + C4H10(g) ∆H= +2657.4kJ/mol
4C(s) + 4O2(g) → 4CO2(g) ∆H= 4(-393.5kJ/mol)
5H2(g) + 2½O2(g) → 5H2O(g) ∆H= 5(-241.8kJ/mol)
______________________________________________________________________
Rule 3: ∆H = -125.6kJ/mol
The value of ΔH for a reaction is the same whether it occurs in one
step or in a series of steps.
 3. Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) DH = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) DH = -296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DH0rxn = -1072 kJ
1. Write the enthalpy of formation reaction for CS2

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

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

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

DH = -393.5 + (2x-296.1) + 1072 = 86.3 kJ
Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of
benzene combusted? The standard enthalpy of formation
of benzene is 49.04 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DHrxn
0
= S nDH0f (products) - S nDH0f (reactants)

DHrxn
0
= [ 12DH0f (CO2) + 6DH0f (H2O)] - [ 2DHf0 (C6H6) ]

DHrxn
0
= [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

6.5
 Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
6.7