1.

4 Enthalpy

What is chemical energy?

• Chemical energy is a form of potential energy which is stored in chemical bonds.

• Chemical bonds are the attractive forces that bind atoms together.
• As a reaction takes place, bonds break in the reactants and new bonds are formed in the
products.
• The difference in energies of the bonds between the atoms of reactants and products is
called chemical energy.

Enthalpy, H

• Enthalpy, H, is the heat energy that is stored in a chemical system, as reactants or

products.
• It is impossible to measure the enthalpy content of a system directly but we can measure
the differences in enthalpy contents.
• The difference in enthalpy contents is the energy either given out or absorbed.

• The energy exchanged with the surroundings can be given out as light, sound, electrical
but is more usually heat.
• This change in enthalpy content is called enthalpy change, DH.

1
Conservation of energy (First Law of thermodynamics)

Energy cannot be created or destroyed just transferred between the system and the
surroundings

• The surroundings, water, tube, air, either gains the energy given out by the system (getting
hot)
• Or the surroundings, water, tube, air loses energy to the system (getting cold) - like ethanol
evaporating from your hand
• This means that:

Heat loss in a Heat gain to the Temperature

=
chemical system surroundings increases
Heat gain in a Heat loss to the Temperature
=
chemical system surroundings decreases

• What your thermometer is measuring is the surroundings. That is - the water, tube, air the
energy is transferred from / to.

Enthalpy change, DH:

Enthalpy Change, DH:

Is the change in heat energy at constant pressure

• This is the difference between the enthalpy contents of the products and the reactants at
constant pressure:

DH = Hproducts - Hreactants

• It is rare for enthalpy contents of products and reactants to be exactly equal.

• This means that there is almost always a transfer of energy between the system and the
surroundings.

2
Exothermic reactions:

• This means that the enthalpy content of the products is smaller than the reactants.
• The excess energy is transferred from the system to the surroundings - hot

Hproducts < Hreactants

DH = Hproducts - Hreactants
DH = Small - Large
DH = Negative value

Energy is transferred from the system to

the surroundings

Endothermic reactions:

• This means that the enthalpy content of the products is greater than the reactants.
• The excess energy is transferred to system from the surroundings - cold

Hproducts > Hreactants

DH = Hproducts - Hreactants
DH = Large - Small
DH = Positive value

Energy is transferred to the system

from surroundings

3
Exothermic and endothermic reactions

1) Combustion of fuels:

• The most common example is the oxidation of methane forming carbon dioxide and water:

CH4(g) + 2O2(g) à CO2(g) + 2H2O(g) DH = - 890 Kj mol-1

• The negative sign means that the reaction is exothermic.

• This means that Hproducts < Hreactants
• The units tell you that 890 Kj of energy is given out per mole of methane.
• Changes in enthalpy are given in molar quantities:

2) Respiration:

• An important exothermic reaction providing energy for all living things:

C6H12O6(aq) + 6O2(g) à 6CO2(g) + 6H2O(l) DH = -2801 Kj mol-1

• The negative sign means that the reaction is exothermic.

• This means that Hproducts < Hreactants
• The units tell you that 2801 Kj of energy is given out per mole of sugar.
• Changes in enthalpy are given in molar quantities:

Endothermic reactions:
1) Photosynthesis:

• An important endothermic reaction without which there would be no life.

6CO2(g) + 6H2O(l) à C6H12O6(aq) + 6O2(g) DH = +2801 Kj mol-1

• The reverse reaction of respiration.

• The positive sign means that the reaction is endothermic.
• This means that Hproducts > Hreactants
• The units tell you that 2801 Kj of energy is taken in per mole of sugar made.
• Changes in enthalpy are given in molar quantities:

2) Thermal decomposition of limestone:

• Limestone contains calcium carbonate:

CaCO3(s) à CaCO(s) + CO2(g) DH = +178 Kj mol-1

• The positive sign means that the reaction is endothermic.

• This means that Hproducts > Hreactants
• The units tell you that 178 Kj of energy is taken in per mole of calcium carbonate.
• Changes in enthalpy are given in molar quantities:

4
Enthalpy profile diagrams

Activation energy:

Activation Energy, Ea
Is the minimum energy required to start a reaction by the
breaking of bonds

• Most reactions do not occur 'spontaneously' but need a little bit of energy to get them
going, a spark is needed to set methane alight.
• This 'bit of energy' is called the activation energy. It is the energy required to break the
bonds in the reactants.

Exothermic reactions: Endothermic reactions:

Exothermic reactions: Endothermic reactions:

Where Hproducts < Hreactants Where Hreactants > Hproducts

DH = negative DH = positive
• Even though the products are lower
• The products are higher in energy than
in energy than the reactants, a small
the reactants, a small amount of energy
amount of energy is needed to
is still needed to break the reactant
break the reactant bonds, the
bonds, the activation energy.
activation energy.
• The reaction has to overcome the energy
• We say the reaction has to
barrier.
overcome the energy barrier.
• This time there is no excess energy to
• After that, the exothermic nature of
break more reactant bonds, a sustained
the reaction is enough to break
amount of energy needs to be continually
more reactant bonds.
supplied to keep the reaction going.
• A way of thinking of this is like a
• This time the cyclist rides a bike up a
cyclist riding a bike up a small hill to
large hill to gain a small amount of 'free
gain a large amount of 'free
wheeling' or energy.
wheeling' or energy.

5
Standard enthalpy changes
Standards:
• Enthalpy changes for reactions will vary slightly depending upon the conditions under which
the reaction is carried out.
• Chemists use standard conditions to ensure that all reactions and corresponding enthalpy
changes are carried out under the same conditions.
• They are as close to normal lab conditions as possible.

Standard conditions, q :

P = 100 kPa

1 Mole or 1 Molar solutions

Normal physical states at standard temperature and pressure

Temperature at 298K (25oC)

Written as:

DH q 298

D - Change in

H - Enthalpy

q symbol represents standard conditions

298 Represents 298K

Standard states:

• Standard enthalpy changes must have substances in their standard states under these
standard conditions:

Chemical symbol and

Substance Explanation
state
Magnesium Mg(s) Magnesium is a solid under standard conditions, (s)
Hydrogen H2(g) Hydrogen is a gas under standard conditions, (g)
Water H2O(l) Water is a liquid under standard conditions, (l)

6
Bond enthalpies

Bond enthalpy:

Bond Enthalpy
Is the energy required to break one mole of a given covalent
bond in the molecule in the gaseous state

Breaking bonds = Energy is put in to break bonds Endothermic process

Forming bonds = Energy released when bonds are formed Exothermic process

Examples:

H - H(g) à 2H(g) DH = +436 KjMol-1

H - Cl(g) à H(g) + Cl(g) DH = + 432 KjMol-1

Bond enthalpies are always positive values as bonds are always broken – Energy is always
put in to break the bonds

Mean bond enthalpy:

• Bonds like C - H exist in all hydrocarbons but their bond enthalpies will vary slightly
depending on their environment:

• For this reason we use Mean bond enthalpies:

Bond Average bond

enthalpy / KJ Mol-1
C-H +413
O=O +497
O-H +463
C=C +612
H-H +436

Mean bond enthalpy:

Mean bond Enthalpy

Is the average value for the bond enthalpy over the range of
compounds it is found in

7
Breaking and making bonds:

• In this and any reaction, reactant bonds will be broken and new product bonds will be
formed.
• When bonds are broken energy is required making it an endothermic process, the
activation energy.
• When new bonds are formed energy is release making it an exothermic process.

Exothermic or endothermic reactions:

Exothermic:

• If the energy released when new bonds form making the products is greater than the
energy needed to break the bonds of the reactants, the reaction is exothermic.

Ein Breaking weak bonds < Eout Forming strong bonds Exothermic process

Endothermic:

• If the energy released when new bonds form making the products is less than the energy
needed to break the bonds of the reactants, the reaction is endothermic.

Ein Breaking strong bonds > Eout Forming weak bonds Endothermic process

8
Using bond enthalpies to determine enthalpy changes:

Energy required to break bonds = S (Bond enthalpies of bonds broken)

Breaking weak bonds = S (Bond enthalpies of bonds formed)

Formula:

S (Bond enthalpies of S (Bond enthalpies of bonds

DH = -
bonds broken) formed)

Worked example:

à à

S (Bond enthalpies of S (Bond enthalpies of

bonds broken) bonds formed)

Reactants Products
Bond Number Bond Total Bond Number Bond Total
energy energy
C-H 4 413 1652 C=O 2 805 1610
O=O 2 497 994 O-H 4 463 1852
S (Bond enthalpies of bonds 2646 S (Bond enthalpies of bonds 3462
broken) = formed) =

DH = S (Bond enthalpies of bonds broken) - S (Bond enthalpies of bonds formed)

DH = 2646 - 3462
DH = - 816 Kj Mol-1

• These values are often less accurate as the mean value and not the actual bond
enthalpies are used.

9
Questions:

1) Calculate the enthalpy change for the reaction:

H2(g) + Br2(g) à 2HBr(g)

Bond H–H Br – Br H – Br
Mean bond enthalpy / Kj Mol-1 +438 +193 +366

2) Calculate the enthalpy change for the reaction:

C4H10(g) + 6.5O2(g) à 4CO2(g) + 5H2O(g)

Bond C–H C–C O=O C=O O–H

Mean bond enthalpy / Kj Mol-1 +413 +347 +497 +805 +463

3) Calculate the enthalpy change for the reaction:

N2(g) + 3H2(g) à 2NH3(g)

Bond N2 H–H N–H

Mean bond enthalpy / Kj Mol-1 +945 +436 +391

10
Types of standard enthalpy changes:

• There are 3 standard enthalpy changes that you need to know:

1) Standard enthalpy change of formation, DfHq

The enthalpy change that occurs when 1 mole of a compound

is formed from its constituent elements in their standard states
under standard conditions.

H2(g) + ½O2(g) à H2O(l)

• DfHq of an element must be zero

• The more negative a DfHq the more stable that compound is.

2) Standard enthalpy of combustion – DcHq

The enthalpy change that occurs when 1 mole of a compound

reacts completely with oxygen under standard conditions
where all reactants and products are in their standard states.

CH4(g) + 2O2(g) à CO2(g) + 2H2O(l)

3) Standard enthalpy change of reaction, DrHq

The enthalpy change when a reaction occurs in the molar

quantities shown in the equation under standard conditions
where all reactants and products are in their standard states.

Fe2O3(s) + 2Al(s) à 2Fe(s) + Al2O3(s)

• For this enthalpy change we need a reaction to refer to.

Questions on standard enthalpy of formation, DfHq:

1) Write the equations for the standard enthalpy change of formation, DfHq for the
following:

a) à C2H4(g)

b) à C4H9Br(l)

c) à K2CO3(s)

11
2) Write the equations for the standard enthalpy change of formation, DfHq for the
following:

a) Propane

b) Sulphuric acid

c) Potassium nitrate

3) Ammonia is made by the Haber process and the equation is shown below

N2(g) + 3H2(g) à 2NH3(g) DH = -93 KJ mol-1

a) What is the enthalpy change of formation of ammonia?

b) 170g of ammonia is made. What is the enthalpy change to make this amount of ammonia?

c) What is the enthalpy change for the decomposition of 10 moles of ammonia?

Questions on standard enthalpy of combustion, DcHq:

4) Write the equations for the standard enthalpy change of combustion, DcHq for the
following:

a) C5H12(l) à

b) C4H9OH(l) à

c) C6H12O6(s) à

12
5) Write the equations for the standard enthalpy change of combustion, DcHq for the
following:

a) Propane

b) Ethene

c) Ethanol

6) Methane is used in the homes as a gas supply for heating and has an enthalpy change
of combustion, DcHq = -882 Kj mol-1

a) Write a balance chemical equation for the enthalpy change of combustion of methane.

b) What is the enthalpy change of combustion when 160g of methane undergoes complete
combustion?

c) What mass of methane would be required to produce 4.41 Kj of energy when it undergoes
complete combustion?

Questions on standard enthalpy of reaction, DrHq:

7) The reaction below is used for welding in isolated places (railway lines)

Fe2O3(s) + 2Al(s) à 2Fe(s) + Al2O3(s) DrHq = -849 Kj mol-1

a) What is the enthalpy change per mole of Iron, Fe?

b) What is the enthalpy change for the production of 1 tonne of Iron, Fe?

13
Determination of enthalpy changes - calorimetry

• Enthalpy content of reactants and products cannot be measured directly.

• You can measure the enthalpy change between the reactants and products - enthalpy
change for a reaction.

Remember:

Heat loss in a Heat gain to the Temperature

=
chemical system surroundings increases
Heat gain in a Heat loss to the Temperature
=
chemical system surroundings decreases

• The enthalpy change for any reaction, DrH is measured in KJ mol-1, which is energy per
mole. This means we need to know 2 things:

i) The energy change - for which we use temperature change and mass of stuff the
heat energy is exchanged between

ii) The amounts in moles of the limiting reagent

Calorimetry – Enthalpy changes involving solutions:

• A calorimeter is an insulated reaction vessel which

minimises heat exchange to the air.
• We use the water as the surroundings so we measure
the amount of energy exchanged with the water.
• The simplest calorimeter is a polystyrene cup but they
can get quite complex.

14
Calculating DT to avoid heat loss errors:

• The initial solution is added and the

temperature taken for 3 minutes.
• On the 4th minute the other solution or
solid is added but temperature not
recorded.
• 5 – 15 minutes the temperature is
recorded.
• The points are extrapolated to the 4
minute mark and the two
temperatures read off the axis.
• This is DT.

Calculation

Step 1: The energy change, q:

q = m c DT

q Quantity of energy exchanged, joules (divide by 1000 converts J to kJ)

m Mass / volume of the water grammes (g = cm3 as the density of water is 1 gcm-3)

c Specific heat capacity j g-1 K-1 (water = 4.18)

DT Change in temperature K,

• As enthalpy is in Kj mol-1 and q is in j, convert the energy calculated by dividing by 1000).

Step 2: Calculate the number of moles used:

Moles = Mass or C x V (dm3)

Mr

Step 3: Calculate the enthalpy, DH:

Enthalpy, DH = Energy, q
Moles

Step 4: Check you have the sign correct:

(-)ve for exothermic reactions

(+)ve for endothermic reactions

15
Example:

Mg is added to 100cm3 of 2.00 Mol dm-3 CuSO4, the temperature rose from 20.0oC to 65oC.

Step 1: The energy change, q:

q = m c DT

q = 100 x 4.18 x 45

q = 18810 joules

q = 18.81 Kj

Step 2: Calculate the number of moles used:

Moles = C x V (dm3)

Moles = 2 x 0.1

Moles = 0.200

Step 3: Calculate the enthalpy, DH:

Enthalpy, DH = Energy, q
Moles

DH = 18.81
0.2

DH = 94.05 Kj mol-1

Step 4: Check you have the sign correct:

(-)ve for exothermic reactions

(+)ve for endothermic reactions

DH = – 94.05 Kj mol-1

16
Questions:

1) Ca is added to 50 cm3 of 1.00 Mol dm-3 H2SO4, the temperature rose from 20.0oC to 40oC.
Calculate the enthalpy change for this reaction:

Step 1: The energy change, q:

q = m c DT

Step 2: Calculate the number of moles used:

Moles = C x V (dm3)

Step 3: Calculate the enthalpy, DH:

Enthalpy, DH = Energy, q
Moles

Step 4: Check you have the sign correct:

DH =

2) 50 cm3 of 2.00 Mol dm-3 HCl was added to 50 cm3 of 2.00 Mol dm-3 NaOH, the temperature
rose from 22.0oC to 47oC. Calculate the enthalpy change for this reaction:

17
Determination of enthalpy changes of combustion - calorimetry

• The enthalpy change of combustion, DcH is measured in KJ mol-1, which is energy per
mole. The calculation follows the same process:

• To calculate DcH, measure a known mass (volume) of

water.
• The temperature rise of the water.
• Weigh the burner before heating.
• Heat to raise the temperature.
• Take a final temperature.
• Reweigh the burner to get a mass of fuel used.

Example: 1.5g of propan-1-ol heated 250cm3 of water by 45oC.

Step 1: The energy change, q:

q = m c DT

q = 250 x 4.18 x 45

q = 47025 joules

q = 47.025 Kj

Step 2: Calculate the number of moles used:

Moles = mass
Mr

Moles = 1.5
60

Moles = 0.025

Step 3: Calculate the enthalpy, DH:

Enthalpy, DcH = Energy, q

Moles

DcH = 47.025
0.025

DcH = 1881 Kj mol-1

Step 4: Check you have the sign correct: Always (-)ve as combustion is always exothermic

DcH = – 1881 Kj mol-1

18
Questions:

1) 2.3 g of ethanol was burned in air. The heat energy increased the temperature of 100 cm3 of
water by 50oC. Calculate the enthalpy change for this combustion reaction:

Step 1: The energy change, q:

q = m c DT

Step 2: Calculate the number of moles used:

Moles = mass
Mr

Step 3: Calculate the enthalpy, DH:

Enthalpy, DcH = Energy, q

Moles

Step 4: Check you have the sign correct:

DcH =

2) 1.1 g of propane was burned in air. The heat energy increased the temperature of 200 cm3 of
water by 25oC. Calculate the enthalpy change for this combustion reaction:

19
Comparison of experimental value with standard enthalpy change:

Standard enthalpy change of combustion of C3H7OH, DcHq298 - 2021 Kj Mol-1

Experimental enthalpy change of combustion of C3H7OH, DcH - 1881 Kj Mol-1

Sources of errors:

• Heat absorbed by the container

• Heat loss to the surroundings

• Incomplete combustion of the fuel - less heat energy given out

• Evaporation of the fuel

Improvements:

• Use a Bomb calorimeter (left).

• This apparatus reduces heat loss s the
water is insulated from the
surroundings.
• It is burnt in oxygen to ensure complete
combustion.

20
Hess's law:

Measuring enthalpy changes indirectly:

• Sometimes it is not possible to measure an enthalpy change directly due to:

High activation energy

Slow rate of reaction

• Hess's law allows us to work out enthalpy changes that are not possible to measure:

Hess’s Law:

The total enthalpy change for a reaction is independent of the

route taken.

• If this was not true, it could be possible to gain energy via route A instead of going via route
B. This would break the 1st law of thermodynamics.
• The total energy for each route is the same: These are called Enthalpy cycles.

Using Hess’s law – Enthalpy cycles

• Enthalpy cycles are used to determine enthalpy changes for reactions that are not easily
measured directly.
• This can be done in 2 ways:

1. Enthalpy changes of formation

2. Enthalpy changes of combustion

21
1) Calculating enthalpy changes from Enthalpy changes of formation, DfHq

• Enthalpy changes of formation can be used in an enthalpy cycle to work out enthalpy
changes.
• Consider the reaction:

2SO2(g) + O2(g) à 2SO3(g)

• The enthalpy cycle would be:

• we use the opposite sign for - 594 = + 594 as our route, Route 2 goes the opposite
direction to the enthalpy cycle

Route 2 = + 594 + - 882

Route 2 = - 288 Kj Mol-1

Remember

Route 1 = Route 2

Route 1 = - 288 Kj Mol-1

Using the formula:

DH = S DfHq (products) - S DfH q (reactants)

DH = (2 x - 441) - (2 x - 297)

DH = - 288 Kj Mol-1

Key point: Look at the table of data à Formation à Arrows up

22
2) Calculating enthalpy changes from Enthalpy changes of combustion, DcHq

• Consider the enthalpy change below:

3C(s) + 4H2(g) à C3H8(g)

• Combustion reactions can be used to find this enthalpy change as carbon hydrogen and
propane all burn in oxygen.
• Constructing an enthalpy cycle:

• we use the opposite sign for - 2219 as our route, Route 2 goes in the opposite direction
to the enthalpy cycle

Route 2 = - 2326 + + 2219

Route 2 = - 107 Kj Mol-1

Remember

Route 1 = Route 2

Route 1 = - 107 Kj Mol-1

Using the formula:

DH = S DcHq (reactants) - S DcHq (products)

DH = (3 x - 394) + (4 x - 286) - - 2219

DH = - 107 Kj Mol-1

Key point: Look at the table of data à Combustion à Arrows down

23
Other enthalpy cycles:
• As long as there is a link between reactants and products, Hess's law can be applied and
enthalpy cycles can be constructed.
• Follow the principles as outlined above and you won't go wrong.

Summary of enthalpy cycles:

Step 1:- Write a balanced chemical equation for the reaction.

Step 2:- Construct the Enthalpy cycle.

Formation à Arrows up
Combustion à Arrows down

Step 3:- Decide on your routes and draw them on the cycle

Step 4:- Write in the DHq for each compound / element next to the arrows.

Step 5:- Look up the values of each DHq and write them in. Add them up for each route.

Step 6:- Write out Hess’s law – Route 1 = Route 2

Step 7:- Put in your numbers.

Step 8:- Calculate DHq

24
Questions:

1) Calculate the enthalpy change for the following reaction given the information in the table
below:

CH4 CH3Cl HCl

q
DfH -74.8 -134.5 -92.3

CH4(g) + Cl2(g) à CH3Cl(g) + HCl(g)

2) Calculate the enthalpy change of formation of ammonia given the information below:

H2(g) + ½O2(g) à H2O(l) DHq = -288 Kj mol-1

4NH3(g) + 3O2(g) à 2N2(g) + 6H2O(l) DHq = -1530 Kj mol-1

25
 3) For the following questions you will need the information in the table below:

H2O(l) CO2(g) C2H6(g) C2H4(g)

q
DfH -285.5 -393 -83.6 +52.0

a) Write equations for the complete combustion of

i) Ethane

ii) Ethene

iii) hydrogen

b) Calculate the enthalpy of combustion in each case using the data above in the table.

26
4) Calculate the enthalpy change for the reaction below given the information in the table
below:

CH3CH2CH2CH3 CH3CH2CH=CH2 H2
q
DcH -2877 -2717 -286

CH3CH2CH=CH2 + H2 à CH3CH2CH2CH3

5) Calculate the enthalpy change of formation of butane, C4H10 given the information in the
table below:

C(s) graphite H2 (g) C4H10 (g)

q
DcH -393.6 -285.9 -2877.1

4C(s) + 5H2(g) à C4H10(g)

27
6) Given the following data:

CH4(g) + 2O2(g) à CO2(g) + 2H2O(l) DH = -890 kJmol-1

CO(g) + 1/2O2(g) à CO2(g) DH = -284 kJmol-1

C(s) + O2(g) à CO2(g) DH = -393 kJmol-1

H2(g) + 1/2O2(g) à H2O(l) DH = -286 kJmol-1

Calculate:

a) The enthalpy of formation of methane

b) The enthalpy change when methane is burned in limited oxygen to form carbon monoxide and
water.

c) The enthalpy of formation of carbon monoxide

28
 Required Practical 2 – Measurement of an enthalpy change

• Hess’s Law can be used to find an enthalpy change that cannot be measured directly:

DH3 = DH1 - DH2

Measuring DH1 and DH2 directly:

1) Weigh 3.90 – 4.10 of anhydrous copper sulphate in a dry stoppered weighing bottle.
2) Place 25cm3 of water into a polystyrene cup and record its initial temperature, t=0

3) Record the temperature for 3 minutes.

4) On the 4th minute add the anhydrous copper sulphate but do not record the temperature.
5) Stir continuously.
6) 5 – 15 minutes the temperature is recorded.
7) Re weigh the stoppered flask to determine the actually mass of anhydrous copper sulphate
added.
8) Plot a graph (as shown above)
9) The points are extrapolated to the 4 minute mark.
10) DT is determined from the graph by reading off the Y axis.

Repeat the experiment for hydrated copper sulphate except:

1) Use between 6.20 – 6.30g of hydrated copper sulphate

2) Use 24cm3 of water. The waters of crystallisation will make the volume up to 25cm3

29
Recording results:

DH1 Mass (g) 2dp DH2 Mass (g) 2dp

Mass of sample and weighing bottle
Mass of weighing bottle
Mass of sample

Time (mins) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
DH1 Temp (oC)
DH2 Temp (oC)

Calculation

Step 1: The energy change, q:

q = m c DT

• As enthalpy is in Kj mol-1 and q is in j, convert the energy calculated by dividing by 1000).

Step 2: Calculate the number of moles used:

Moles = Mass or C x V (dm3)

Mr

Step 3: Calculate the enthalpy, DH:

Enthalpy, DH = Energy, q
Moles

Step 4: Check you have the sign correct:

(-)ve for exothermic reactions

(+)ve for endothermic reactions

Use your answers to DH1 and DH2 to calculate DH3 using Hess’s law

DH3 = DH1 - DH2

30