Hess's Law part 2

Doing the questions

As was mentioned in part 1, most of the questions are based upon enthalpy of formation or enthalpy of
combustion.

However, they do occasionally throw in other examples but they tend to be quite easy.

Enthalpy of Formation

The triangle

The first thing to do with these questions is:

look for the data to see which type of question it is

The table below shows enthalpies of formation, so we are going to base this question on formation.

Hf/KJ mol-1
CO2(g) -393.5
H2O(l) -285.8
CH3OH(l) -239.1

As was mentioned at the end of the previous part of this tutorial, the triangle is just three normal
equations. And as this question is based on formation, everything in the table must be a product.

You are forming (making) CO2, H2O and CH3OH. This means you draw arrows towards these compounds.

The information in the table could be written as several equations:

C(s) + O2(g) CO2(g)

H2(g) + O2(g) H2O(l)

C(s) + 2H2(g) + O2(g) CH3OH(l)

So draw arrows towards CO2, H2O and CH3OH. You also need to know the definition of formation i.e.
forming the compounds from the elements.

Therefore we need the elements as reactants. Remember the equations are telling you this!
With formation questions, we write the elements on the bottom line (as shown above) and the arrows
are drawn from the elements (upwards).

we have said that the example above is a formation example. But note that the top line is
combustion! This can cause a lot of confusion. Ignore the type of enthalpy change on the top line, it
is irrelevant when constructing the triangle.

all the equations in the triangle should be balanced with state symbols, as it is above.

Calculating the value

The question is asking us to work out the enthalpy of combustion of methanol (H1) (it usually is the top
line that you are trying to work out but not always).

Here is the cycle again. In terms of working out the final value, the important equation to balance is H1,
the others are just there for completeness.

As was discussed in part 1, the easiest way to know which arrows to add together is to compare it to the
original cycle:
We can see that the blue H2 arrow in the formation example, is pointing the wrong way, therefore we
can say that:

H1 = -H2 + H3
Or if you prefer:

H1 = H3 H2

putting in the numbers to calculate H1 SHOULD be easy but be very careful to take into account the
numbers in front of the elements in the top line.

H2 in this case is only the enthalpy of formation of CH3OH. From the table this value is -239.1 kJ mol-1

elements do not have an enthalpy of formation.

H3 is the enthalpy of formation of CO2 AND the enthalpy of formation of H2O.

We need -393.5 for the CO2 and 2 x -285.8 for the H2O, adding those together gives us:

2 x -285.8 + (-393.5) = -965.1 kJ mol-1

Therefore:

H1 = H3 - H2

= -965.1 (-239.1) = -726 kJ mol-1

Id advise writing out each step like this as it minimizes mistakes and it also shows the examiner that you
know what youre doing. Students often get the signs mixed up at some point, which is caused by trying
to do too much too quickly.

Enthalpy of Combustion
This time we are going to use enthalpy of combustion data that is given to us.

Hc/KJ mol-1
C(s) -394
H2(g) -286
CH3COOH(l) -870
Remember that the triangle is just normal equations turned on their side. From the data above, we are
combusting C, H2 and CH3COOH. This means that they are all reactants. Therefore we must draw an
arrow from them.

And again, we need to know the definition of combustion. Combustion means we form CO2 and H2O.
Therefore draw arrows from the reactants and write in CO2 and H2O on the bottom line:

to balance the equations for combustion, it is common to have to write O 2 on the H2 and H3
arrows.

Alternatively, writing out the combustion equations to work out which way the arrows point:

2C(s) + 2O2(g) 2CO2(g) (combustion of carbon)

and 2H2(g) + 2O2(g) 2H2O(l) (combustion of hydrogen)

CH3COOH(l) + 2O2(g) 2CO2(g) + 2H2O(l) (combustion of ethanoic acid)

The equations show you that the arrows go TOWARDS the combustion products of CO2 and H2O, and
these products are always the same for combustion reactions.

Calculating the value

As was said in example 1, the most important line to balance is H1 in terms of getting the correct
numerical value.

To work out H1, we can again compare the combustion triangle above with the original triangle:

We can see that the H3 arrow in the combustion example is pointing the wrong way.
Therefore, we can say that
H1 = H2 - H3

H2: enthalpy of combustion of carbon AND enthalpy of combustion of hydrogen:

2 x -394 + (2 x -286) = -1360 kJ mol-1

H3 is simply the enthalpy of combustion of methanol: -870 kJ mol-1

Therefore:
H1 = -1360 (-870) = -490 kJ mol-1

A few conclusions
From the two examples above we can see that there are only TWO ways that the arrows go, either
towards or away from the bottom line.

The top line is the important line to balance in terms of getting the correct value but you may have to
balance all the equations depending on the question.

We can simplify all of this further by stating that:

H formation questions: H1 = (products - reactants)

H combustion question: H1 = (reactants - products)