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TOPIC 5: ENERGETICS/THERMOCHEMISTRY

5.1 Measuring energy changes

Syllabus:

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Understandings:

Heat is a form of energy:

Heat:

• Measures total energy in a given amount of substance

Temperature is a measure of the average kinetic energy of the particles:

Temperature:

• Measures average kinetic energy of substance

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Total energy is conserved in chemical reactions:

First law of thermodynamics:

• Total energy is conserved in chemical reactions

• Cannot be created nor destroyed – can only be transferred

Chemical reactions that involve transfer of heat between the system and the surroundings are
described as endothermic or exothermic:

Chemical reactions:

• Energy is required to break bonds in reactants

• Energy is given out when new bonds are formed in products
• The most important type is heat
Type of reaction Exothermic Endothermic
Definition Gives out heat to surroundings Absorbs heat from surroundings
Bond strengths Stronger in products than Weaker in products than

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reactants reactants

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Examples Combustion, neutralisation Photosynthesis
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The enthalpy change (∆H) for chemical reactions is indicated in kJ mol-1:

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Enthalpy (H):
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• Measures internal energy stored in the reactants

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• Absolute value of reactants/products cannot be known

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• Instead, the enthalpy change can be calculated

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Enthalpy change (ΔH):

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• Measured as kJ of energy released/absorbed per mole

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• Negative for exothermic reactions

• Positive for endothermic reactions
• When enthalpy change is negative, the products become more stable with lower stored
energy
• Thus, expected that most reactions occur this way
• However, endothermic reactions still occur, as products may become more disordered (e.g.
gas produced from 2 solids/liquids)
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Calculating enthalpy changes:

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• 𝑞 = 𝑚𝑐∆𝑇

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• q = heat evolved (J)
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• m = mass (g)
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• c = specific heat capacity (J/g/K)

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• ∆T = temperature change (K)

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• Should be expressed in kJ/mol:

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o Convert from J to kJ (divide by 1000)

o Divide by number of moles of limiting reagent
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o Make negative - if it is exothermic reaction

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• The specific heat capacity (c) of water is 4.18 J/g/K

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o Requires 4.18 joules to raise 1g of water by 1K

∆H values are usually expressed under standard conditions, given by ∆H°, including standard states:

Standard conditions:

• Standard conditions are 100kPa pressure and 298K temperature

Standard enthalpy change (∆H θ ):

• Enthalpy change when 1 mole of a compound is formed from its elements in their standard
states at 298K and 100kPa
• Standard states: at 25oC and 1mol/dm3
Gases Liquids Solids

H2 (g) Br (l) Si (s)

N2 (g) Hg (l) C (graphite)

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O2 (g) Group 1 & 2 metals

F2 (g) Ni/Cu/Zn/Ag

Cl2 (g)
• Gives a measure of the stability of a substance relative to its elements
• ∆Hfθ for an element in its standard state will be 0
• θ
∆𝐻(𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠) = (∆Hf(products) θ
) − (∆Hf(reactants) )
Standard enthalpy change of combustion:

• 1 mole of a substance is completely combusted in oxygen under standard conditions

A calorimetry experiment for an enthalpy of reaction should be covered and the results evaluated:

Calorimetry:

• Process of measuring heat of a chemical reaction

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• All the heat evolved in an exothermic reaction is used to heat a known mass of water
• Endothermic reactions would cause a lowered temperature
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Temperature against time is extrapolated to measure temperature rise if the reaction was
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instantaneous
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o Compensates for heat lost by water to surroundings as reaction proceeds

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Assumptions:
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• All of heat from reaction is transferred to water

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Density of water is 1.00g/cm3

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• No heat energy is lost

• Combustion reaction is complete
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• There is no change in state

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Possible errors:

• Not all energy might transfer to/from water

• Heat is lost from water as insulation is not perfect (e.g. using a glass beaker instead of a
polystyrene cup with lid)
• Altitude affects water density (not necessarily at STP)
• Solutes affect water density and thus specific heat capacity
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5.2 Hess’s Law

Syllabus:

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Understandings:
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The enthalpy change for a reaction that is carried out in a series of steps is equal to the sum of the
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enthalpy changes for the individual steps:

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Hess’s Law:
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• Enthalpy change for a reaction depends only on the difference between the enthalpy of the
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products and reactants

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• It is independent fo the reaction pathway

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• Can determine enthalpy changes which cannot be directly measured

Example 1:

• Enthalpy of combustion of carbon/carbon monoxide into carbon dioxide can be measured

• However, the combustion of carbon into carbon monoxide cannot
• Can be solved via simultaneous equations and Hess's Law
e.g.

1. C (s) + O2 (g) --> CO2 (g), ∆H = -394 kJ/mol

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2. CO (g) + 0.5O2 (g) --> CO2 (g), ∆H = -283 kJ/mol

• Subtract 2 from 1:
• C (s) + O2 (g) - CO (g) - 0.5O2 (g) --> CO2 (g) - CO2 (g)
• C (s) + 0.5O2 (g) - CO (g) = 0, ∆H = −394 − (−283) kJ/mol
• Rearrange equation: C (s) + 0.5O2 (g) --> CO (g), ∆H = -111 kJ/mol
Example 2:

• Calculate the standard enthalpy change when 1 mole of methane is formed from its
elements in their standard states.
• The standard enthalpies of combustion ∆Hcθ of carbon, hydrogen, and methane are -394, -
286, and -890 kJ/mol respectively.

∆Hθ
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• C(s) + 2H2 (g) → CH4 (g)

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• ∆Hcθ (C) + 2∆Hcθ (H2 ) = ∆Hxθ + ∆Hcθ (CH4 )

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• ∆Hxθ = ∆Hcθ (C) + 2∆Hcθ (H2 ) − ∆Hcθ (CH4 )

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• ∆Hxθ = −394 + (2 × −286) − (−890) kJ/mol

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• ∆Hxθ = −76 kJ/mol

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5.3 Bond enthalpies

Syllabus:

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Understandings:
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Bond-forming releases energy and bond-breaking requires energy:

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Bond formation:
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• Negative value – energy is evolved

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Bond breaking:
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• Positive value – energy is put in

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Average bond enthalpy is the energy needed to break one mol of a bond in a gaseous molecule
averaged over similar compounds:

Bond enthalpy:

• Amount of energy required to break 1 mole of a bond in gaseous molecule into atoms
• 𝑋 − 𝑌 (𝑔) ↔ 𝑋 (𝑔) + 𝑌 (𝑔)
• E.g. CH4 (g) --> C (g) + 4H (g)
• Can be known for simple diatomic molecules with 2 atoms
• If bond enthalpy values are known for all bonds in reactants and products, overall enthalpy
change can be calculated

Average bond enthalpy:

• Energy needed to break 1 mole of a bond in gaseous molecules, averaged over similar
compounds
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Limitations of bond enthalpies:

• Can only be used if all reactants/products are in gaseous state

• E.g. if water was liquid, more heat would be evolved for vaporisation of water
• Energy of a particular bond will vary in different compounds (is an average of the same bond
over different compounds)

Discussion of the bond strength in ozone relative to oxygen in its importance to the atmosphere:

Oxygen:

• Present in two forms – normal oxygen (O2) and ozone (O3)

• Both protect Earth from harmful UV radiation
• They are converted from one to the other
• The O=O bond in O2 is stronger than the O-O in O3

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Breaking bonds:
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• Bonds are broken when UV radiation of sufficient energy is absorbed
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• O=O bonds are broken by radiation of higher energy/shorter wavelength than O-O
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• The ozone layer protects the Earth by absorbing both high and low energy UV light to break
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these bonds
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Breaking double bonds:

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• In the stratosphere, UV radiation with a shorter wavelength (less than 242 nm) breaks the
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O=O double bond in O2

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o Endothermic – absorbs energy

•
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Forms 2 oxygen free radicals (uncharged with unpaired electrons)

o O2 (g) --> 2O• (g), λ < 242 nm
• 1 highly reactive free radical reacts with another O2 molecule to form ozone
o O• (g) + O2 (g) --> O3 (g)
o Exothermic – heats stratosphere
• Ozone is broken down again as more UV is absorbed
o O3 (g) --> O• (g) + O2 (g), λ < 330 nm
• Ozone can also be broken down when reacted with free radical (albeit slower)
o O3 (g) + O• (g) --> 2O2 (g)

• The concentration of ozone remains constant

• The reactants are at a standard state
• The rate of ozone formation is balanced by the rate of removal

Chlorofluorocarbons (CFCs):

• Stable in lower atmosphere

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• However, release free radicals after absorbing UV light in the stratosphere

• Halogen free radicals prevent oxygen radicals from making ozone

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