Enthalpy changes

When chemical reactions occur, there is a change in energy. Energy has many forms examples are heat, light, sound and
electrical. The most obvious of these is the transfer of heat.

Exothermic and Endothermic

Chemical reaction which release energy to the surrounding are called exothermic and the ones which absorb energy
from the surrounding are called endothermic

1. Classify each of the following s exothermic and endothermic

a. The burning of magnesium in air
b. The crystallization of copper sulfate from a saturated solution
c. The thermal decomposition of magnesium nitrate
d. The fermentation of glucose by yeast
e. The evaporation of water

Enthalpy changes and enthalpy profile diagrams

We call the energy exchange between a chemical reaction and its surroundings at constant pressure, the enthalpy
change. Enthalpy is the total energy associated with the reactants, we cannot measure total enthalpy but we can
measure enthalpy change. The symbol of enthalpy is H. and of enthalpy change is ∆H.

We can draw enthalpy profile diagram, to show enthalpy changes. The enthalpy of the reactants and products is shown
on the Y axis.

2. Draw enthalpy profile diagrams for

a. The combustion of sulfur to form sulfur dioxide
b. The endothermic reaction

H2O (g) + C (s) H2 (g) + CO (g)

For Head Start School

Standard enthalpy
G - 8 Achanges
level’s Branch

Standard conditions 0331-4200252

To make any comparisons of enthalpy changes, we must usethe same conditions. These are called standard conditions.
 • A pressure of 105 Pa or 1 atm.
• A temperature of 298oK or 25oC.
• Each substance involved in the reaction is in its normal physical estate.

The symbol of Ө shows that this reaction is carried out under standard conditions.

A variety of enthalpy changes

Standard enthalpy change of reaction. ∆Hᶿr
The standard enthalpy change of a reaction is the enthalpy change which occurs when equation quantities of materials
react under standard conditions, and with everything in its standard state

2H2 (g) + O2 (g) 2H2O (l) ∆Hᶿr = -572 kJ/mol

Standard enthalpy change of formation. ∆Hᶿf

The standard enthalpy change of formation of a compound is the enthalpy change which occurs when one mole of the
compound is formed from its elements under standard conditions, and with everything in its standard state.

H2 (g) + ½ O2 (g) H2O (l) ∆Hᶿf = -286 kJ/mol

Standard enthalpy change of Combustion. ∆Hᶿc

The standard enthalpy change of combustion of a compound is the enthalpy change which occurs when one mole of the
compound is burned completely in oxygen under standard conditions, and with everything in its standard state.

C2H6 (g) + 3 ½ O2 (g) 2CO2 (g) + 3H2O (l) ∆Hᶿc = -1560 kJ/mol

H2 (g) + ½ O2 (g) H2O (l) ∆Hᶿf = -286 kJ/mol

3. Classify each of the following reactions as ∆Hᶿr, ∆Hᶿf or ∆Hᶿc

a. MgCO3 (s) MgO (s) + CO2 (g)
b. C(graphite) + O2 (g) CO2 (g)
c. HCl (g) + NH3 (g) NH4Cl (s)
d. H2 (g) + ½ O2 (g) H2O (l)

Standard enthalpy change of Neutralization. ∆Hᶿn

The standard enthalpy change of neutralization is the enthalpy change when solutions of an acid and an alkali react
together under standard conditions to produce 1 mole of water.

HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l) ∆Hᶿn = -57.1 kJ/mol

Standard enthalpy change of Solution. ∆Hᶿsol

The enthalpy change of solution is the enthalpy change when 1 mole of an ionic substance dissolves in water to give a
solution of infinite dilution under standard conditions.

NaOH (s) + aq NaOH (aq) ∆Hᶿsol = -44.1 kJ/mol

Standard enthalpy change of atomization. ∆Hᶿatm
The standard atomization enthalpy is the enthalpy change when 1 mole of gaseous atoms is formed from the element in
its standard state. Enthalpy change of atomization is always positive.

½ H2 (g) H (g) ∆Hᶿatm= +218kJ/mol

Measuring enthalpy changes

Calorimetry
When carrying out experiments in calorimeter (calorimeter is basically an insulated cup, the below picture shows a
polystyrene cup) we use known amounts of reactants and known volumes of
liquids. We also measure the temperature change of the liquid in the calorimeter
as the reaction occurs. Calorimeter relies on the fact that it takes 4.18 J of energy
required to raise the temperature 1 g of liquid by 1oC. This is called the specific
heat of water. Its 4.18 Jg-1mol-1. The energy given out is calculated by the
relationship q = mc∆T, Where

• Q is the energy transferred , in J

• M is the mass of water , in g
• C is the specific heat capacity, in Jg-1C-1
• ∆T is the change in temperature, in Co

4. a. Calculate the energy transferred when the temperature of 75cm3 of water rises from 23oC to 54oC
b. When 8g of sodium chloride is dissolved in 40 cm3 the temperature of water falls from 22 oC to 20.5 oC.
calculate the energy absorbed by the solution when sodium chloride dissolves
c. A student added 50 cm3 of sodium hydroxide to 50cm3 of HCl. Both solutions were at 18oC to start
with. When the solutions were mixed a reaction occurred. The temperature rose to 33oC. calculate the
energy released in this reaction.

Enthalpy change of neutralization by experiment

We can find enthalpy change of neutralization of NaOH with HCl as follow

• Place 50cm3 of 1.0 mol/dm3 HCl in the cup and record the temperature
• Add 50cm3 of 1.0 mol/dm3 NaOH (at the same temperature) to the acid in the cup
• Stir the reaction mixture with the thermometer and record the highest temperature

In this experiment most of the heat is transferred to the solution since the cup is an insulator. Cooling of the warm
solution is not a problem, since reaction is rapid, so the maximum temprature is reached before much cooling of the
warm solution has occurred. However there are still heat losses to the air and to the thermometer which makes the
results less exothermic than the data booklet value of 57.1 kJ/mol

Results & conclusions

Mass of solution = 100g (50cm3 + 50cm3, assuming 1 cm3 = 1g)

Specific heat capacity = 4.18 Jg-1oC-1

Starting Temperature = 21.3oC

Final Temperature = 27.8oC

Temperature Rise = 6.5oC

Use the relationship = mc∆T

Heat energy released = 100 x 4.18 x 6.5 = 2717 J

So 2717 J of energy is released by 50cm3 of 1.0 mol/dm3 HCl & NaOH, the number of moles of each is calculated by
concentration x volume (in cm3) /1000 = 1.0 x 50 / 1000 = 0.050 moles

So 2717 J of energy was released by 0.05 moles of acid, 1 mol acid will produce 2717/0.050 = -54340 J/mol. The negative
sign shows the reaction is exothermic.

5. Explain why the enthalpy change of neutralization of one mole of H2SO4 is not the standard enthalpy change of
neutralization.

Enthalpy change of solution by experiments

The enthalpy change of solution of NaOH can be found using a calorimeter. We use known amounts of solute and
solvents in excess to make sure that all the solute dissolves. The procedure is :

• Weigh an empty polystyrene cup

• Pour 100 cm3 of water into the cup and weigh the cup and water
• Record the steady temperature of the water with thermometer reading to the least nearest 0.2oC
• Add a few pellets of NaOH which has been stored under dry conditions
• Keep the mixture stirred continuously with a thermometer and record the temperature at fixed intervals e.g.
every 20 sec
• Keep recording the temperature for 5 min after the maximum temperature has been reached
• Weigh the cup and its contents to calculate the mass of NaOH

Results and Calculations

Mass of polystyrene cup = 23.00g

Mass of polystyrene cup + water = 123.45g

Mass of water = 100.45g

Mass of cup + water + sodium hydroxide = 124.95g

Sodium hydroxide that dissolved = 1.50g

Initial temperature of water = 18.0oC

Final temperature of water = 21.6oC

Temperature rise = 3.6oC

From the results, 1.50 g of NaOH is dissolved in 100.45 cm3(100.45g) of water and produced a temperature rise of 3.6oC.

Energy transferred as heat (in J) = mass of water (in g) x specific heat (Jg-1oC-1) x temperature change (in oC)

= 100.45 x 4.18 x 3.6 = 1511.57J = 1.5 kJ

1.5 g of NaOH releases 1.5 kJ of energy on dissolving

I mol of NaOH (Mr=40gmol-1) = 40/1.5 x 1.5kJ = 40 kJ

∆Hᶿsol = - 40 kJ/mol

6. A student added 10g (0.25 mol) of NaOH to 40 cm3 of water to make a concentrated solution. All the NaOH
dissolved. He measured the maximum temperature rise. He suggested that these results would give an
accurate value for the standard enthalpy change of solution. Give 2 reasons why he is incorrect.

Finding enthalpy change of combustion

We can find the enthalpy change of combustion by burning a known mass of substance and using the heat released to
raise the temperature of a known mass of water. The procedure is

• Weigh the spirit burner containing propan-1-ol. The cap on the burner must be kept on
when the burner is not burning, to avoid evaporation of the fuel.
• Pour 100 cm3 (100g) of water into the calorimeter. For greater accuracy you should
weigh it
• Stir the water and record temperature with a thermometer to at least nearest 0.1oC
• Place the burner beneath the calorimeter, remove the cap and light the wick. The length
of the wick should have been previously adjusted so that the material of the wick does not burn
and the flame just touches the bottom of the calorimeter.
• Keep stirring the water with the thermometer until there is a raise of 10oC
• Remove the spirit burner, place the cap on the it and re-weigh it.

Results and calculation

To find the enthalpy change of combustion w need to know

• The mass of fuel burnt

• The temperature raise of the water
• The mass of water
• The Mr of the fuel.

Mass of water in calorimeter = 100g

Mass of spirit burner and propan-1-ol at start = 86.27
Mass of spirit burner and propan-1-ol at end = 86.06
Mass of fuel burnt = 0.21 g
Initial temperature of water = 30.9oC
Final temperature of water = 20.0oC
Temperature raise of water = 10.7 oC
Using relation q=mc∆T = 100x4.18x10.7 =4472.6J
So the energy release by 0.21 g is 4472.6J, heat released by 60g of fuel (Mr of prop-1-ol=60g) will be 4472.6x60/0.21
= 1277885.7 J/mol=1300kJ/mol
This is much less than the data book value of -2021kJ/mol mainly due to heat losses to surrounding.

7. A student calculated the standard enthalpy change of combustion of ethanol ∆Hᶿc [C2H5OH] by Calorimetry as -
870 kJ/mol. The data book value is -1367kJ/mol. Explain the reason for the difference.

Hess’s Law
Hess’s law states that the total enthalpy changes in a chemical reaction are independent of the route by which the
chemical reaction takes place as long as the initial and final conditions are the same.
Enthalpy cycles
We can illustrate Hess’s law by drawing
enthalpy cycles. Let’s consider the
Indirect Route following cycle

In the enthalpy cycle on the left, there

is one direct route, A + B converting to
C. then there are indirect routes, A + B
Direct Route first converting to X then X converting
to Y + Z, and finally Y + Z converting to
C. in the other indirect way you can see
A + B converting to F + G, and F + G
converting to C. we can use Hess’s law
to calculate enthalpy changes that
cannot be found by experiments using
calorimeter.
Indirect Route

Enthalpy changes of reaction from enthalpy changes of formation

We can calculate the enthalpy changes of reaction by the cycle above. We use the enthalpy changes of formation of the
reactants and products to find the enthalpy change of
reaction. For the above cycle if we apply Hess’s law we
see that

∆H2 = ∆ H1 + ∆Hr

Worked Example
Calculate the standard enthalpy change for the below
reaction

2NaHCO3 (s) Na2CO3 (s) + CO2 (g) + H2O (l)

The relevant enthalpy changes are

∆Hᶿf [NaHCO3 (s)] = -950.8 kJ/mol

∆Hᶿf [Na2CO3 (s)] = -1130.7 kJ/mol

∆Hᶿf [CO2 (g)] = -393.5 kJ/mol

∆Hᶿf [H2O (l)] = -285.8 kJ/mol

Using Hess’s law

∆H2 = ∆ H1 + ∆Hr

∆Hᶿf [Na2CO3 (s)] + ∆Hᶿf [CO2 (g)] + ∆Hᶿf [H2O (l)] = 2∆Hᶿf [NaHCO3 (s)] + ∆Hr

∆Hr = (-1130.7) + (-393.5) + (-285.8) -2(-950.8) = -1810.0 + 1901.6 = + 91.6 kJ/mol

Note

• The value for ∆Hᶿf [NaHCO3 (s)] is multiplied by 2 because 2 moles NaHCO3 appear in the solution.
• The values of ∆Hᶿf [Na2CO3 (s)], ∆Hᶿf [CO2 (g)] and ∆Hᶿf [H2O (l)] are added together to give H2 take account of that
fact that some values may be positive and some may be negative.

8. a. Draw an enthalpy cycle to calculate ∆Hᶿr for the reaction

2Al (s) + Fe2O3 (s) 2Fe (s) + Al2O3 (s)
• Calculate ∆Hᶿr using the following data

∆Hᶿf [Fe2O3 (s)] = -824.2 kJ/mol

∆Hᶿf [Al2O3 (s)] = -1675.7 kJ/mol

Enthalpy change of formation from enthalpy changes of combustion

We can calculate the enthalpy change of formation of many compounds by using a different enthalpy cycle as below

elements + oxygen compound formed + oxygen

combustion products

Applying Hess’s law we get

∆H1 = ∆ H2 + ∆Hf

To calculate the enthalpy change of formation using this type of cycle

 • Write the equation for enthalpy change of formation at the top; add oxygen on both sides to balance the
combustion reactions
• Draw the cycle with the combustion products at the bottom
• Draw in all arrows making sure they go in correct directions
• Apply Hess’s law & taking in account the number of moles of each reactant and product.

Worked example
Calculate the standard enthalpy change of formation of C2H6. The relevant enthalpy changes of combustion are

C (graphite) + O2 (g) CO2 (g) ∆Hᶿc [C (graphite)] = -393.5 kJ/mol

H2 (g) + ½ O2 (g) H2O (l) ∆Hᶿc [H2 (g)] = -285.8 kJ/mol

C2H6 (g) + 3 ½ O2 (g) 2CO2 (g) + 3H2O ∆Hᶿc [C2H6 (g)] = -1559.7 kJ/mol

The enthalpy cycle is below

Using Hess’s law ∆H1 = ∆ H2 + ∆Hf

2(-393.5) + 3(-285.5) = ∆Hf + (-1559.7)

∆Hf = -1644.4 – (-1559.7) = -84.7kJ/mol

9. Draw an enthalpy cycle to calculate the enthalpy change of formation of ethanol C2H5OH, using enthalpy
changes of combustion
• Calculate the value for ∆Hᶿf [C2H5OH (l)] using the following data

∆Hᶿc [C (graphite)] = -393.5 kJ/mol

∆Hᶿc [H2 (g)] = -285.8 kJ/mol

∆Hᶿc [C2H5OH (g)] = -1367.3 kJ/mol

Calculating the enthalpy change of hydration of an anhydrous salt
We can calculate this by using the following cycle, all you need to know is the standard enthalpy change of solution for
both anhydrous and hydrated salt. Consider the below cycle

Anhydrous Salt Hydrated Salt

Dilute Aqueous solution of Salt

The enthalpy cycle for calculating the enthalpy of hydration of sodium thiosulphate is shown in figure below

Na2S2O3(s)+5H2O(l) ∆Hhyd
Na2S2O3.5H2O (s)

Na2S2O3 (aq)
Using Hess’s law ∆H1= ∆Hhyd + ∆H2, ∆Hhyd = ∆H1 - ∆H2

∆Hhyd = -7.6 – (+47.4) = - 55.0 kJ/mol

10. Suggest why it is difficult to measure the enthalpy changes directly when an anhydrous salt is converted to a
hydrated salt.

Bond Energies and enthalpy changes

Bond breaking and bond making

Enthalpy changes re due to the formation and breaking of bonds. Breaking bonds require energy; the energy is needed
to overcome the attractive forces among the atoms. Energy is released when bonds are formed. Bond making is
exothermic and bond breaking is endothermic
 • If the energy needed to break bonds is less than the energy released when new bonds are formed, the
reaction is exothermic.
• If the energy needed to break bonds is more than the energy released when new bonds are formed, the
reaction is endothermic.

CH4 (g) ∆Hhyd C(g) + 4H(g)

C(graphite) + 2H2(g)

11. use the information is above figure and the information below to show that the averagebond energy of C-H
bond is 415.9 kJ/mol

∆Hᶿf [CH4] = -74.8 kJ/mol

∆Hᶿatm[1/2 H2] = +218 kJ/mol

∆Hᶿatm[C (graphite)] = + 716.7 kJ/mol

Calculating enthalpy changes using bond energies

We can use bond enthalpies to calculate the enthalpy change of a reaction that we cannot measure directly, for example
the reaction for Born Haber process.

N2 (g) + 3H2 2NH3 (g)

The enthalpy cycle for this reaction is shown in the figure below

2 H-N-H(g)
NΞN(g) + 3H-H(g)
H

2N(g)+ 6H(g)
It is often easier to set out the calculations as a balance sheet as shown below. The relevant bond energies are

E (NΞN) = 945 kJ/mol

E (H-H) = 436 kJ/mol

E (N-H) = 391 kJ/mol

Bonds Broken ∆H1(kJ) Bonds Formed ∆H2(kJ)

1 x NΞN = 1 x 945 = 945 6 x N-H = 6x391
3 x H-H = 3 x 436 = 1308
Total = +2253 Total = -2346

Notice in these calculations that:

• One triple bond in nitrogen is broken

• three single bonds in hydrogen are broken
• Six single N-H bonds are formed, there are 2 ammonia molecules, in each molecule there are 3 N-H bonds.
• Values for bond breaking are positive as its endothermic, values for bond making are negative showing its
exothermic

From the cycle we can say ∆Hf = ∆H1 + ∆H2

∆Hf = 2253 -2346 = -93 kJ/mol

12. The equation for the combustion of ethanol is

C2H5OH (g) + 3O2 (g) 2CO2 (g) + 3H2O (l) ∆Hᶿc [C2H5OH (g)] = -1559.7 kJ/mol

a. Rewrite the equation to show all the bonds in the reactant and products
b. Use the following bond energies (in kJ/mol) to calculate a value for the standard enthalpy change of
this reaction

E (C-C) = +347 kJ/mol

E (C-H) = +410 kJ/mol

E (C-O) = +336 kJ/mol

E (O=O) = +496 kJ/mol

E (C=O) = +805 kJ/mol

E (O-H) = +465 kJ/mol

c. The standard enthalpy change of combustion of ethanol is -1367.3 kJ/mol. Suggest why this value
differs from the value obtained using bond energies.