4.

6 Representing thermochemical cycles

5 Reverse the sign of t::. 1 H 0 if the red arrow is in the opposite

direction to the black arrow.
6 Go round che cycle in the direction of the red arrows and add up
che llH 9 values as you go.
Hess's law shows that this is the same as t::.H 6 for the direct reaction .

.lH
CH30CH3(g} - ­ --­ C2H50H (I)
1
methoxymethane ethar'Ol

,,~
4
/,,,
4.

- 184 kJ mol f\ / ~77 kJ mol I

5.
2C (s, graphite) + 3H2 (g) + \.!z 02 (g) 277 kJ mol 1
+184kJmo1-1
elements
2.
6. 6.H~ = + 184 ­ 277
-93 kJ mol 1

.A. Figure 2 Thermochemical cycle for the formation of ethanolfrom methoxymethane

Using an enthalpy diagram

The following steps are shown in red on th e e nthalpy diagram.
1 Draw a line at level 0 to represent the elements.
2 Look up the values of t::. 1H" for each compound and encer these
on the enthalpy diagrams, taking account of che signs - negative
values are below 0, positive values are above.
3 Find the difference in levels between the two compounds. This
represents the difference in their enthalpies.
4 t::.T-f' is the difference in levels taking account ofthe diredion ofchange.
Up is positive and down is negative. From methoxymethane
to ethanol is down so the sign is n ega tive. From ethanol to
methoxymethane the sign of t::.H9 would be positive.

l
enthalpy 277 kJ mo1 -1
l 84kJmol I

-184 ,_

3 93kJmol 1
_ ,___ _;_
2_____H
. ~HsO__
(I)_ _ ____,_
277
Study tip
.A. Figure 3 The enthalpy diagram for the formation ofethanolfrom methoxymethane
Remember that you do not need to
draw these diagrams accurately Notice how the enthalpy level diagram makes it much clearer
to scale but a rough scale is than the thermochemical cycle that e thanol has less energy than
important to ensure that the methoxymethane. This means that it is the more e nergetically stable
relative levels are correct. compound. The values of!::.~ for the reaction are the same whichever
method you use .

.
 Energetics

I
Example 2 Hint rx
To find l!.H 9 for the reaction NH 3 (g) + HCl(g) NH 4 Cl(s)
You can use a short cut to save
The standard molar enthalpy changes of formation of the compounds are: drawing an enthalpy diagram or a
NH 3 !!. 1 H9 = -46 kJ mol- 1 thermochemical cycle. The enthalpy
change of a reaction is the sum of
HCI A, fl° =-92 kJ mo1- 1 the enthalpies of formation of all
NH4 CI !!. 1 H'' = -314kJ mol- 1 the products minus the sum of the
enthalpies offormation of all the
Using a thermochemical cycle reactants. In this example
The thermochemical cycle for the formation of ammonium chloride is
M/ 0 = -314-(-46 + (-92))
shown in Figure 4.
=-314- [-138)
I Write an equa tio n for the reaction. = -1?6 kJ mo1- 1.
2 Write down the elemen ts that make up the two compounds with
If you use this short cut, you must
the correct quanti ties of each.
be very careful of the signs.
3 Put in the !!. 1 H9 values with arrows showing the direction, that is,
from elements 10 compounds.
4 Put in the arrows going from the starting materials to products via
the elements (the red arrows).
0
5 Reverse the sign o f Ar H H the red arrow is in the opposite
direction to the black arrow(s).
6 Go round the cycle in the direction of the red arrows and add up
the values of flH° as you go.

3. 3.
4. .). j.lrf .).rH" 4.
-46kJf -92 kJ 11101-1 - 314kJ11101-1

+138 kJ rnol · (i~N2(g) + 2H2(g) + ~Cl2(g)~ -314 kJmo1 ­ 1

2.
.). H·= +46+92+ 314kJ rnol I
- - 176kJ rnol 1

• Figure 4 Thermochemical cyclefor the formation ofammonium chloride

Using an enthalpy diagram

The following steps are shown in red on the enthalpy diagram.

1 Draw a line at level Dto represent the elements.

2 Draw in NH 4 CI 314 kJ mo1­ 1 below this.
3 Draw a line representing ammonia 46 kJ mo1- 1 below the level of the
elements. (There is still tH 2 and tc1 2 1eft unused.)
4 Draw a line 92 kJ mo1­ 1 below ammonia. This represents hydrogen
chloride.
5 Find the difference in levels between the (NH 3 + HCI) line and the NH 4 CI
6
one. This represents AH for the reaction. As the change from (NH 3 + HCI)
9
to NH4 CI is down, AH must be negative.