ENERGY TRANSFERS IN CHEMICAL

REACTIONS

KEYWORDS: Activation energy … Breaking a chemical bond …

Bond energy explained … Bond energy calculations
(theoretical) ... calculations (practical) ... Catalyst action …
Chemical bond … Endothermic reaction … Energy level
diagrams … Exothermic reaction … Experimental methods for
determining energy changes ... Reaction profiles ... Making a
chemical bond

Heat Changes in Chemical Reactions

 When chemical reactions occur, as well as the formation of the products, there is
also a heat energy change which can often be detected as a temperature change.
 This means the products have a different energy content than the original
reactants (see the reaction profile diagrams below).
 If the products contain less energy than the reactants, heat is given out to the
surroundings and the change is called exothermic. The temperature of the system will
be observed to rise in an exothermic change.
o Examples:
 the burning or combustion of hydrocarbon fuels
 the burning of magnesium, reaction of magnesium and acid or reaction
of sodium on water
 the neutralisation of acids and alkalis
 using hydrogen as a fuel in fuel cells
 If the products contain more energy than the reactants, heat is taken in (absorbed)
from the surroundings and the change is called endothermic. If the change can take
place spontaneously, the temperature of the reacting system will fall but in some cases
the reactants must be heated to speed up the reaction and provide the absorbed heat.
o Examples:
 the thermal decomposition of limestone)
 the cracking of oil fractions
 The difference between the energy levels of the reactants and products gives
the overall energy change for the reaction.
 At a more advanced level the heat change is called the enthalpy change is denoted by
delta H, H.
o If H is negative (-ve) for exothermic ie heat energy is being lost from the
system,
o an H is positive (+ve) for endothermic ie heat energy is being gained by the
SYSTEM
 EXOTHERMIC ENDOTHERMIC

Combustion Decomposition of Limestone

CH4 + 2O2→ CO2 + 2H2O CaCO3 → CaO + CO2

∆H = -822kJ/mole ∆H = 222kJ/mole
Haber Process ( Formation of Decomposition of Silver Chloride by
Ammonia ) light
N2 + 3H2 ↔ 2NH3 2AgCl →2Ag + Cl2

∆H = -184kJ/mole ∆H = 254kJ/mole
Contact Process; Industrial Prep. of Photosynthesis
Sulphuric Acid 6CO2 + 6H2O →C6H12O6 + 6O2
2SO2 + O2 ↔ 2SO3
∆H = 2816kJ/mole
∆H = -189kJ/mole

Reduction of Iron III oxide in Blast

Furnace
Fe2O3 + 3CO → 2Fe + 3CO2

∆H = -27kJ/mole

o system.

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 Note on Reversible Reactions
 If the direction of a reversible reaction is changed, the energy change is also
reversed.
 For example: the thermal decomposition of hydrated copper(II) sulphate.
 On heating the blue solid, hydrated copper(II) sulphate, steam is given off and the
white solid of anhydrous copper(II) sulphate is formed.
o This a thermal decomposition and is endothermic as heat is absorbed
(taken in)
o The energy is needed to break down the crystal structure and drive off the
water.
 When the white solid is cooled and water added, blue hydrated copper(II) sulphate is
reformed.
o The reverse reaction is exothermic as heat is given out.
o ie on adding water to white anhydrous copper(II) sulphate the mixture heats up
as the blue crystals reform.

blue hydrated copper(II) sulphate + heat white anhydrous copper(II)

sulphate + water

CuSO4.5H2O(s) CuSO4(s) + 5H2O(g)

Activation Energy and Reaction Profiles

 When gases or liquids are heated the particles gain kinetic energy and move faster
increasing the chance of collision between reactant molecules.
 However this is not the main reason for the increased reaction speed because most
molecular collisions do not result in chemical change.
 Before any change takes place on collision, the colliding molecules must have a minimum
kinetic energy called the Activation Energy. Do not confuse it with the overall energy
change also shown in the diagrams below.

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 It does not matter whether the reaction is an exothermic or an endothermic energy
change. Heated molecules have a greater kinetic energy and more of them will then have
the required activation energy to react.
 The increased chance of higher energy collisions greatly increases the speed
of the reaction.
 The activation energy 'hump' can be related to the bond breaking and making
processes.
o Up the hump is endothermic, representing breaking bonds (energy absorbed,
needed to pull atoms apart),
o down the other side of the hump is exothermic, representing bond formation
(energy released, as atoms become electronically more stable).

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 Catalysts and Activation Energy
 Catalysts increase the rate of a reaction by helping break chemical bonds in
reactant molecules.
 This effectively means the Activation Energy is reduced (see diagram 'humps' below).
 Therefore at the same temperature, more reactant molecules have enough kinetic
energy to react compared to the uncatalysed situation and so the reaction speeds up
with the greater chance of a 'fruitful' collision.
 Although a true catalyst does take part in the reaction, it does not get used up and
can be reused with more reactants.
 However a solid catalyst might change physically by becoming more finely divided,
especially if the reaction is exothermic.
 Also note from the diagram that although the activation energy is reduced, the overall
exothermic or endothermic energy change is the same for both the catalysed or
uncatalysed reaction. The catalyst might help break the bonds BUT it cannot change the
actual bond energy

Calculation of heat transfer using bond

energies
 Atoms in molecules are held together by chemical bonds which are the electrical
attractive forces between the atoms.
 The bond energy is the energy involved in making or breaking bonds and is usually
quoted in kJ per mole of the particular bond involved.

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 To break a chemical bond requires the molecule to take in energy to pull atoms
apart, which is an endothermic change. The atoms of the bond vibrate more until they
spring apart.
 To make a chemical bond, the atoms must give out energy to become combined
and electronically more stable in the molecule, this is an exothermic change.
 The energy to make or break a chemical bond is called the bond energy and is quoted
in kJ/mol of bonds.
o Each bond has a typical value eg to break 1 mole of C-H bonds is on average
about 413kJ,
o the C=O takes n average 743 kJ/mol, and note the stronger the bond, the more
energy is needed,
o and not surprisingly, a typical double bond needs more energy to break than a
typical single bond.
 During a chemical reaction, energy must be supplied to break chemical bonds in the
molecules, this the endothermic 'upward' slope on the reaction profile on diagrams
above.
 When the new molecules are formed, new bonds must be made in the process, this is
the exothermic 'downward' slope on the reaction profile on diagrams above.
 If we know all the bond energies of the molecules involved in a reaction, we can
theoretically calculate what the net energy change is for that reaction and determine
whether the reaction is exothermic or endothermic.
 We do this by calculating the energy taken in to break the bonds in the reactant
molecules. We then calculate the energy given out when the new bonds are formed. The
difference between these two gives us the net energy change.
o In a reaction energy must be supplied to break bonds (energy absorbed, taken
in, endothermic).
o Energy is released when new bonds are formed (energy given out, releases,
exothermic).
o If more energy is needed to break the original existing bonds of the reactant
molecules, than is given out when the new bonds are formed in the product
molecules, the reaction is endothermic.
o If less energy is needed to break the original existing bonds of the reactant
molecules, than is given out when the new bonds are formed in the product
molecules, the reaction is exothermic.
o So the overall energy change for a reaction ( H) is the overall energy net
change from the bond making and bond forming processes. These ideas are
illustrated in the calculations below.

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 Example 1. Hydrogen + Chlorine ==> Hydrogen Chloride
o The symbol equation is: H2(g) + Cl2(g) ==> 2HCl(g)
o but think of it as: H-H + Cl-Cl ==> H-Cl + H-Cl
o (where - represents the chemical bonds to be broken or formed)
o the bond energies in kJ/mol are: H-H 436; Cl-Cl 242; H-Cl 431
o Energy needed to break bonds = 436 + 242 = 678 kJ taken in
o Energy released on bond formation = 431 + 431 = 862 kJ given out
o The net difference between them = 862-678 = 184 kJ given out (92 kJ per
mole of HCl formed)
o More energy is given out than taken in, so the reaction is exothermic.

 Example 2. Hydrogen Bromide ==> Hydrogen + Bromine

o The symbol equation is: 2HBr(g) ==> H2(g) + Br2(g)
o but think of it as: H-Br + H-Br ==> H-H + Br-Br
o (where - represents the chemical bonds to be broken or formed)
o the bond energies in kJ/mol are: H-Br 366; H-H 436; Br-Br 193
o Energy needed to break bonds = 366 + 366 = 732 kJ taken in
o Energy released on bond formation = 436 + 193 = 629 kJ given out
o The net difference between them = 732-629 = 103 kJ taken in (51.5kJ per
mole of HBr decomposed)
o More energy is taken in than given out, so the reaction is endothermic

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 Example 3. hydrogen + oxygen ==> water
o 2H2(g) + O2(g) ==> 2H2O(g)
o or 2 H-H + O=O ==> 2 H-O-H (where - or = represent the
covalent bonds)
o bond energies in kJ/mol: H-H is 436, O=O is 496 and O-H is 463
o bonds broken and energy absorbed (taken in):
 (2 x H-H) + (1 x O=O) = (2 x 436) + (1 x 496) = 1368 kJ
o bonds made and energy released (given out):
 (4 x O-H) = (4 x 463) = 1852 kJ
o overall energy change is:
 1852 - 1368 = 484 kJ given out (242 kJ per mole hydrogen burned or
water formed)
 since more energy is given out than taken in, the reaction is
exothermic.
o NOTE: Hydrogen gas can be used as fuel and a long-term possible
alternative to fossil fuels (see methane combustion below in example
5..
 It burns with a pale blue flame in air reacting with oxygen to be oxidised
to form water.
 hydrogen + oxygen ==> water or 2H2(g) + O2(g) ==> 2H2O(l)
 It is a non-polluting clean fuel since the only combustion product is
water and so its use would not lead to all environmental problems
associated with burning fossil fuels.
 It would be ideal if it could be manufactured by electrolysis of water eg
using solar cells.
 Hydrogen can be used to power fuel cells.

 Example 4. nitrogen + hydrogen ==> ammonia

o N2(g) + 3H2(g) ==> 2NH3(g)

o or N N + 3 H-H ==> 2
o bond energies in kJ/mol: N N is 944, H-H is 436 and N-H is 388
o bonds broken and energy absorbed (taken in):
 (1 x N N) + (3 x H-H) = (1 x 944) + (3 x 436) = 2252 kJ
o bonds made and energy released (given out):
 2 x (3 x N-H) = 2 x 3 x 388 = 2328 kJ
o overall energy change is:
 2328 - 2252 = 76 kJ given out (38 kJ per mole of ammonia formed)
 since more energy is given out than taken in, the reaction is
exothermic.

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 Example 5. methane + oxygen ==> carbon dioxide + water
o CH4(g) + 2O2(g) ==> CO2(g) + 2H2O(g)

o or
o bond energies in kJ/mol:
 C-H single bond is 412, O=O double bond is 496, C=O double bond is
743, H-O single bond is 463
o bonds broken and energy absorbed (taken in from surroundings)
 (4 x C-H) + 2 x (1 x O=O) = (4 x 412) + 2 x (1 x 496) = 1648 + 992 =
2640 kJ taken in
o bonds formed and energy released (given out to surroundings)
 (2 x C=O) + 2 x (2 x O-H) = (2 x 743) + 2 x (2 x 463) = 1486 + 1852 =
3338 given out
o overall energy change is:
 3338 - 2640 = 698 kJ/mol given out per mole methane burned,
 since more energy is given out than taken in, the reaction is
exothermic.
o NOTE: This is the typical very exothermic combustion chemistry of
burning fossil fuels but has many associated environmental problems

 Example 6. analysing the bonds in more complex molecules

o ethyl ethanoate
 2 x C-C single covalent bonds
 8 x C-H single covalent bonds
 2 x C-O single covalent bonds
 1 x C=O double covalent bond

o ethanol
 1 x C-C single covalent bond
 5 x C-H single covalent bonds
 1 x C-O single covalent bond
 1 x O-H single covalent bond
o Heats of combustion can be theoretically calculated like in example 5.

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 The experimental determination of energy changes

This method 1. is can be used for any non-combustion reaction

that will happen spontaneously at room temperature involving liquids
or solid reacting with a liquid. The reactants are weighed in if solid
and a known volume of any liquid (usually water or aqueous
solution). The mixture could be a salt and water (heat change on
dissolving) or an acid and an alkali solution (heat change of
neutralisation). It doesn't matter whether the change is exothermic
(heat released or given out) or endothermic (heat absorbed or taken
in). See calculations below.
This method 2. is specifically for determining the heat energy
released (given out) for burning fuels. The burner is weighed before
and after combustion to get the mass of fuel burned. The
thermometer records the temperature rise of the known mass of
water (1g = 1cm3).

You can use this system to compare the heat output from burning
various fuels. The bigger the temperature rise, the more heat energy
is released. See calculations below for expressing calorific values.

This is a very inaccurate method because of huge losses of heat eg

radiation from the flame and calorimeter, conduction through the
copper calorimeter, convection from the flame gases passing by the
calorimeter etc. BUT, at least using the same burner and set-up, you
can do a reasonable comparison of the heat output of different fuels.

Calculations from the experimental results

 The method described below applies to both experimental methods described
above.
 You need to know the following:
o the mass of material reacting in the calorimeter (or their
concentrations and volume),
o the mass of water in the calorimeter,
o the temperature change (always a rise for method 2. combustion),
o the specific heat capacity of water, (shorthand is SHC water), and this is
4.2J/g/oC,
 this means it takes 4.2 J of heat energy to change the
temperature of 1g of water by 1oC (or K).
 Example 1 typical of method 1.
o 5g of ammonium nitrate (NH4NO3) was dissolved in 50cm3 of water
(50g) and the temperature fell from 22oC to 14oC.
o Temperature change = 22 - 14 = 8oC (endothermic, temperature fall,
heat energy absorbed)
o Heat absorbed by the water = mass of water x SHCwater x temperature
 = 50 x 4.2 x 8 = 1680 J (for 5g)
 heat energy absorbed on dissolving = 1680 / 5 = 336 J/g of
NH4NO3
o this energy change can be also expressed on a molar basis.
 Relative atomic masses Ar: N = 14, H = 1, O = 16

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  Mr(NH4NO3) = 14 + (1 x 4) + 14 + (3 x 16) = 80, so 1 mole =
80g
 Heat absorbed by dissolving 1 mole of NH4NO3 = 80 x 336 =
26880 J/mole
 At AS level this will be expressed as enthalpy of solution =
Hsolution = +26.88 kJmol-1
 The data book value is +26 kJmol-1
 Example 2 typical of method 2.
o 100 cm3 of water (100g) was measured into the calorimeter.
o The spirit burner contained the fuel ethanol C2H5OH ('alcohol') and
weighed 18.62g at the start.
o After burning it weighed 17.14g and the temperature of the water rose
from 18 to 89oC.
o The temperature rise = 89 - 18 = 71oC (exothermic, heat energy given
out).
o Mass of fuel burned = 18.62-17.14 = 1.48g.
o Heat absorbed by the water = mass of water x SHCwater x temperature
 = 100 x 4.2 x 71 = 29820 J (for 1.48g)
 heat energy released per g = energy supplied in J / mass of fuel
burned in g
 heat energy released on burning = 29820 / 1.48 = 20149 J/g of
C2H5OH
o this energy change can be also expressed on a molar basis.
 Relative atomic masses Ar: C = 12, H = 1, O = 16
 Mr(C2H5OH) = (2 x 12) + (1 x 5) + 16 + 16 = 46, so 1 mole =
46g
 Heat released (given out) by 1 mole of C2H5OH = 46 x 20149 =
926854 J/mole
 At AS level this will be expressed as enthalpy of combustion =
Hcomb = -926.9 kJmol-1
 The data book value for the heat of combustion of ethanol is -
1371 kJmol-1, showing lots of heat loss!

DONE

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