Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure

Stoichiometry Involving DH:

Thermochemical Equations

 Enthalpy change is also called enthalpy of

reaction or heat of reaction.
 Extensive property – depends on amount of
material undergoing the reaction
 The amount of heat generated depends on the
amount of reactant or product
 Consider the combustion of propane

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Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure

Example

Consider the combustion of propane:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)

DHrxn = –2044 kJ

This means that 2044 kJ of energy is released for every mol

of propane or every 5 moles of oxygen reacted

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Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure

Example

Consider the combustion of propane:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)

DHrxn = –2044 kJ

Calculate DH in which 5.00 g of propane is burned in excess

oxygen at constant pressure.

1 mol C3H 8  2044 kJ

5.00 g C3H 8 x x = – 232 kJ
44.09 g C3H 8 mol C3H 8
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Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure

Learning Check

Consider the combustion of propane:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)

DHrxn = –2044 kJ

Calculate DH in which 25.0 g of water is released when

propane is burned in excess oxygen at constant pressure.

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 Solution

Consider the combustion of propane:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)

DHrxn = –2044 kJ

Calculate DH in which 25.0 g of water is released when

propane is burned in excess oxygen at constant pressure.

1 mol H2O 1 mol C3H 8  2044 kJ

25.0 g H 2O x x x = – 709 kJ
18.02 g H2O 4 mol H2O mol C3H 8

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 Characteristics of Enthalpy Changes
DHrxn

 The change in enthalpy for a reaction (DHrxn) is

associated with a particular reaction
 If we change the characteristics of the the reaction then
DHrxn changes too
 Lets look at a couple of examples

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 Characteristics of Enthalpy Changes

1. If a chemical reaction is multiplied by some

factor then DHrxn is multiplied by the same
factor.
A + 2B  C DH1

Multiply by 2

2A + 4B  2C DH2 = DH1 x 2

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 Characteristics of Enthalpy Changes

2. If a reaction is reversed, then DHrxn changes

sign.

A + 2B  C DH1

Reverse reaction

C  A + 2B DH2 = – DH1

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 Characteristics of Enthalpy Changes

3. If a chemical reaction can expressed as the sum

of a series of steps, then DHrxn for the overall
equation is the sum of the heats of reactions for
each step.

A + 2B  C DH1
C  2D DH2
–––––––––––––––––––
A + 2B  2D DH3 = DH1 + DH2

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Relationships Involving DHrxn
Hess’s Law

 This last
relationship
is called
Hess’s Law
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Relationships Involving DHrxn
Example of Hess’s Law

 N2(g) + 2O2(g) → 2NO2(g) ΔH1 = 68 kJ

This reaction also can be carried out in two distinct steps with
enthalpy changes designated by DH2 and DH3.

N2(g) + O2(g) → 2NO(g) DH2 = 180 kJ

2NO(g) + O2(g) → 2NO2(g) DH3 = – 112 kJ
N2(g) + 2O2(g) → 2NO2(g) DH2 + DH3 = 68 kJ

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 Example

 Consider the following data:

1 3
NH3 (g)    N2 (g)  H2 (g) DH = 46 kJ
2 2
2 H2 (g)  O2 (g)  
 2 H2O(g) DH =  484 kJ

 Calculate ΔH for the reaction

2 N2 (g)  6 H2O(g)  
 3 O2 (g)  4 NH3 (g)

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Relationships Involving DHrxn
Example
1 3
NH3 (g)    N2 (g)  H2 (g) DH = 46 kJ
2 2
2 H2 (g)  O2 (g)  
 2 H2O(g) DH =  484 kJ

Desired reaction:
2 N2 (g)  6 H2O(g)  
 3 O2 (g)  4 NH3 (g)

Reverse the two reactions:

1 3
N2 (g)  H2 (g)  
 NH3 (g) DH =  46 kJ
2 2
2 H2O(g)  
 2 H2 (g)  O2 (g) DH = +484 kJ
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Relationships Involving DHrxn
Example

 Multiply reactions to give the correct numbers of

reactants and products:
1 
4 DH =  46 kJ
3
4  N2 (g)  H2 (g)  
 NH3 (g) 
2 2 

3 2 H2O(g)  
 2 H2 (g)  O2 (g)  3 DH = +484 kJ

 Desired reaction:
2 N2 (g)  6 H2O(g)  
 3 O2 (g)  4 NH3 (g)

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Relationships Involving DHrxn
Example

 Final reactions:
2 N2 (g)  6 H2 (g)  
 4 NH3 (g) DH =  184 kJ
6 H2O(g)  
 6 H2 (g)  3 O2 (g) DH = +1452 kJ

 Desired reaction:

2 N2 (g)  6 H2O(g)  
 3 O2 (g)  4 NH3 (g)

DH = +1268 kJ

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Relationships Involving DHrxn
Problem-Solving Strategy

 Work backward from the required reaction, using

the reactants and products to decide how to
manipulate the other given reactions at your
disposal.
 Reverse any reactions as needed to give the
required reactants and products.
 Multiply reactions to give the correct numbers of
reactants and products.

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 Learning Check

Two forms of carbon are graphite, the soft, black, slippery material used in
“lead" pencils and as a lubricant for locks, and diamond, the brilliant, hard
gemstone. Using the enthalpies of combustion for graphite (-394 kJ/mol)
and diamond (-396 kJ/mol), calculate ΔH for the conversion of graphite to
diamond.

Cgraphite (s)  Cdiamond (s)

Cgraphite (s) + O 2 (g)  CO 2 (g) DH =  394 kJ

Cdiamond (s) + O 2 (g)  CO 2 (g) DH =  396 kJ

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 Solution

Two forms of carbon are graphite, the soft, black, slippery material used in
“lead" pencils and as a lubricant for locks, and diamond, the brilliant, hard
gemstone. Using the enthalpies of combustion for graphite (-394 kJ/mol)
and diamond (-396 kJ/mol), calculate ΔH for the conversion of graphite to
diamond.

Cgraphite (s)  Cdiamond (s)

Cgraphite (s) + O2 (g)  CO 2 (g) DH =  394 kJ

CO2 (g)  Cdiamond (s) + O2 (g) DH =  396 kJ 
Cgraphite (s)  Cdiamond (s) DH = 2 kJ

The ΔH for the conversion of graphite to diamond is 2 kJ/mole graphite

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Relationships Involving DHrxn
Learning Check

 Find DHrxn for the reaction

 N2O(g) + NO2(g)  3NO(g)

 Using

 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

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Relationships Involving DHrxn
Solution

 Desired Reaction N2O(g) + NO2(g)  3NO(g)

 Reverse eq 1, multiply eq 1 and 3 by 1/2

 ½[2NO2(g)  2 NO(g) + O2(g)] ½[DH = + 113.1 kJ]

 N2(g) + O2(g)  2 NO(g) DH = 182.6 kJ
 ½[2 N2O(g)  2 N2(g) + O2(g)] ½[DH = –163.2 kJ]

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Relationships Involving DHrxn
Solution

 Desired Reaction N2O(g) + NO2(g)  3NO(g)

 Reverse eq 1, multiply eq 1 and 3 by 1/2

 NO2(g)  NO(g) + ½ O2(g) ½[DH = + 113.1 kJ]

 N2(g) + O2(g)  2 NO(g) DH = 182.6 kJ
 N2O(g)  N2(g) + ½ O2(g) ½[DH = –163.2 kJ]

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Relationships Involving DHrxn
Solution

 Desired Reaction N2O(g) + NO2(g)  3NO(g)

 Reverse eq 1, multiply eq 1 and 3 by 1/2

 NO2(g)  NO(g) + ½ O2(g) ½ + 113.1 = 56.55 kJ

 N2(g) + O2(g)  2 NO(g) 182.6 kJ
 N2O(g)  N2(g) + ½ O2(g) ½ –163.2 kJ = –81.6 kJ
 157.6 kJ

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 How many ways are there to determine
DHrxn?

 So far we have looked at two different ways to

determine DHrxn
 Calorimetry – coffee cup calorimeter
 qp = DHrxn
 Hess’s Law – where we infer DHrxn by knowing the
values of DHrxn of our reaction from other reactions with
known values
 Now we will look at a third way

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Determining Enthalpies of Reaction from Standard Enthalpies of Formation
Standard States and Standard Enthalpy
Changes

 The third method to determine DHrxn uses tables of

Enthalpies (or Heats of Formation)
 This method determines the amount of heat required to
make all the reactants and products in something called
the “standard state” and then compares them to each
other.
 So lets talk about standard state.

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 Standard States and Standard Enthalpy
Changes

 DH is the change in enthalpy for a chemical reaction

 The difference in enthalpy between the products and

reactants
 DH = Hproducts – Hreactants

 So the difference in enthalpy is an absolute value (like the

difference in altitude)
 But enthalpy itself (like altitude) is a relative quantity –
defined relative to some standard (such as sea level in the
case of altitude)

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 Standard States and Standard Enthalpy
Changes

 So what are the standards that we use when talk about

enthalpy
 Well there are three – but they are related
 The standard state
 The standard enthalpy change (DH°)
 The standard enthalpy of formation (DHf°)

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 Standard States and Standard Enthalpy
Changes

 Standard State
 For a gas – pure gas at 1 atm of pressure
 For a liquid or solid – pure substance in its most stable form
at 1 atm of pressure and 298 K (25 °C)
 For a solution – 1 M solution

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 Standard States and Standard Enthalpy
Changes

 Standard Enthalpy Change (DH°)

 The change in enthalpy for a process when all reactants
and products are in their standard states.
 Standard Enthalpy of Formation (DHf°)
 For a pure compound – the change in enthalpy when 1
mole of the compound forms from its constituent
elements in their standard states.
 For a pure element in its standard state DHf°= 0

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Determining Enthalpies of Reaction from Standard Enthalpies of Formation
Standard States and Standard Enthalpy
Changes

 When we assign a value of 0 for DHf° to a pure element

in its standard state it is the same thing as assigning sea
level an altitude of 0.
 The interesting thing to notice about the table of
enthalpies (or heats) of formation for compounds is that
most of the values are negative
 Below sea level
 This actually means that compounds have less enthalpy
(more stable) that the original elements that comprised
them.

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Determining Enthalpies of Reaction from Standard Enthalpies of Formation

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 Standard Enthalpy of Formation (DHf°)

 We can use DHf° to calculate DH for a reaction

 Add up all the DHf° for the products
 Because the are being formed
 Subtract all the DHf° of the reactants
 Because they are being broken down
 Pay attention to stoichiometry of equation

DHrxn° = SnpDHf° (products) – SnpDHf° (reactants)

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 Example

Calculate DH° for the following reaction:

2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Given the following information:
DHf° (kJ/mol)
Na(s) 0
H2O(l) –286
NaOH(aq) –470
H2(g) 0
 [2(–470) + 0] – [0 + 2(–286)] = –368 kJ DH = –368 kJ

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 Learning Check

Calculate DH° for the following reaction:

4 NH3 (g) + 7O2(g) → 4 NO2(g) + 6H2O(l)

Use the Table on the next slide.

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4 NH3 (g) + 7O2(g) → 4 NO2(g) + 6H2O(l)

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 Solution

Calculate DH° for the following reaction:

4 NH3 (g) + 7O2(g) → 4 NO2(g) + 6H2O(l)

[4(34) + 6(–286)] – [4(–46) + 0] = –1396 kJ

DH = –1396 kJ

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 Problem-Solving Strategy: Enthalpy
Calculations
1. When a reaction is reversed, the magnitude of ΔH
remains the same, but its sign changes.
2. When the balanced equation for a reaction is multiplied
by an integer, the value of ΔH for that reaction must be
multiplied by the same integer.
3. The change in enthalpy for a given reaction can be
calculated from the enthalpies of formation of the
reactants and products:
DH°rxn = SnpDHf° (products) - SnrHf° (reactants)
4. Elements in their standard states are not included in the
DHreaction calculations because DHf° for an element in its
standard state is zero. 36
 Energy Consumption

 Combustion of Fossil fuels is Highly Exothermic

 Coal C (s) + O2 (g)  CO2 (g)

 DHrxn° = – 393.5 kJ

 Natural Gas CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (g)

 DHrxn° = – 802.3 kJ

 Petroleum C8H18 (l) + 25/2 O2 (g)  8 CO2 (g) + 9 H2O (g)

 DHrxn° = – 5074.1 kJ
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 Environmental Problems Associated with
Fossil Fuel Use

 Non renewable
 Produce greenhouse gases (CO2, H2O)
 Produce other gases from side reactions due to
impurities
 Sulfur oxides – contribute to acid rain
 Nitrogen oxides – contribute to SMOG
 Ozone – ground level ozone is a dangerous pollutant

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