Beruflich Dokumente
Kultur Dokumente
Hess's Law
Stating Hess's Law
Hess's Law is the most important law in this part of chemistry.
Most calculations follow from it. It says . . .
The enthalpy change accompanying a chemical change is
independent of the route by which the chemical change
occurs.
http://www.chemguide.co.uk/physical/energetics/sums.html
1/8
8/17/2016
Hess's Law says that the overall enthalpy change in these two
http://www.chemguide.co.uk/physical/energetics/sums.html
2/8
8/17/2016
routes will be the same. That means that if you already know two of
the values of enthalpy change for the three separate reactions
shown on this diagram (the three black arrows), you can easily
calculate the third - as you will see below.
The big advantage of doing it this way is that you don't have to
worry about the relative positions of everything on an enthalpy
diagram. It is completely irrelevant whether a particular enthalpy
change is positive or negative.
Warnings!
Although most calculations you will come across will fit into a
triangular diagram like the above, you may also come across other
slightly more complex cases needing more steps. That doesn't
make it any harder!
You need to take care in choosing your two routes. The pattern will
not always look like the one above. You will see that in the
examples below.
3/8
8/17/2016
-3267
C(s)
-394
H2(g)
-286
You will notice that I haven't bothered to include the oxygen that the
various things are burning in. The amount of oxygen isn't critical
because you just use an excess anyway, and including it really
confuses the diagram.
http://www.chemguide.co.uk/physical/energetics/sums.html
4/8
8/17/2016
Why have I drawn a box around the carbon dioxide and water at
the bottom of the cycle? I tend to do this if I can't get all the arrows
to point to exactly the right things. In this case, there is no obvious
way of getting the arrow from the benzene to point at both the
carbon dioxide and the water. Drawing the box isn't essential - I
just find that it helps me to see what is going on more easily.
Notice that you may have to multiply the figures you are using. For
example, standard enthalpy changes of combustion start with 1
mole of the substance you are burning. In this case, the equations
need you to burn 6 moles of carbon, and 3 moles of hydrogen
molecules. Forgetting to do this is probably the most common
mistake you are likely to make.
How were the two routes chosen? Remember that you have to go
with the flow of the arrows. Choose your starting point as the
corner that only has arrows leaving from it. Choose your end point
as the corner which only has arrows arriving.
Now do the calculation:
Hess's Law says that the enthalpy changes on the two routes are
the same. That means that:
H - 3267 = 6(-394) + 3(-286)
Rearranging and solving:
H = 3267 + 6(-394) + 3(-286)
H = +45 kJ mol-1
Note: If you have a good memory, you might remember that I
gave a figure of +49 kJ mol-1 for the standard enthalpy
change of formation of benzene on an earlier page in this
section. So why is this answer different?
The main problem here is that I have taken values of the
enthalpies of combustion of hydrogen and carbon to 3
significant figures (commonly done in calculations at this
level). That introduces small errors if you are just taking each
figure once. However, here you are multiplying the error in the
carbon value by 6, and the error in the hydrogen value by 3. If
you are interested, you could rework the calculation using a
value of -393.5 for the carbon and -285.8 for the hydrogen.
That gives an answer of +48.6.
So why didn't I use more accurate values in the first place?
Because I wanted to illustrate this problem! Answers you get
to questions like this are often a bit out. The reason usually
lies either in rounding errors (as in this case), or the fact that
http://www.chemguide.co.uk/physical/energetics/sums.html
5/8
8/17/2016
+52.2
HCl(g)
-92.3
C2H5Cl(g)
-109
Note: I'm not too happy about the value for chloroethane! The
data sources I normally use give a wide range of values. The
one I have chosen is an average value from the NIST
Chemistry WebBook. This uncertainty doesn't affect how you
do the calculation in any way, but the answer may not be
exactly right - don't quote it as if it was right.
In the cycle below, this reaction has been written horizontally, and
the enthalpy of formation values added to complete the cycle.
http://www.chemguide.co.uk/physical/energetics/sums.html
6/8
8/17/2016
Again, notice the box drawn around the elements at the bottom,
because it isn't possible to connect all the individual elements to
the compounds they are forming in any tidy way. Be careful to
count up all the atoms you need to use, and make sure they are
written as they occur in the elements in their standard state. You
mustn't, for example, write the hydrogens as 5H(g), because the
standard state for hydrogen is H2.
And now the calculation. Just write down all the enthalpy changes
which make up the two routes, and equate them.
+52.2 - 92.3 + H = -109
Rearranging and solving:
H = -52.2 + 92.3 - 109
H = -68.9 kJ mol-1
Note: I am afraid that this is as much as I feel I can give you
on this topic without risking sales of my book, or ending up in
breach of contract with my publishers. Unfortunately, it isn't
enough for you to be confident of being able to do these
calculations every time. Apart from anything else, you need
lots of practice.
http://www.chemguide.co.uk/physical/energetics/sums.html
7/8
8/17/2016
I have talked this through more gently in the book, with lots of
examples. If you chose to work through chapter 5 in the
book, you would be confident that you could do any chemical
energetics calculation that you were given.
Obviously I'm biased, but I strongly recommend that you
either buy the book, or get hold of a copy from your school or
college or local library. Don't just take my word for it - read
the reviews on the Amazon website.
http://www.chemguide.co.uk/physical/energetics/sums.html
8/8