VARIOUS ENTHALPY CHANGE DEFINITIONS

This page explains what an enthalpy change is, and then gives a definition and
brief comment for three of the various kinds of enthalpy change that you will
come across. You will find some more definitions on other pages in this section.

It is essential that you learn the definitions. You aren't going to be able to do any
calculations successfully if you don't know exactly what all the terms mean.

Enthalpy changes

Enthalpy change is the name given to the amount of heat evolved or absorbed in
a reaction carried out at constant pressure. It is given the symbol ΔH, read as
"delta H".

Note:  The term "enthalpy change" only applies to reactions done at constant
pressure. That is actually how most lab reactions are done - in tubes or flasks (or
whatever) open to the atmosphere, so that the pressure is constant at
atmospheric pressure.

The phrase "at constant pressure" is an essential part of the definition but, apart
from that, you are unlikely to need to worry about it if you are doing a UK-based
exam at the equivalent of A level.

Standard enthalpy changes

Standard enthalpy changes refer to reactions done under standard conditions,

and with everything present in their standard states. Standard states are
sometimes referred to as "reference states".

Standard conditions

Standard conditions are:

 298 K (25°C)
 a pressure of 1 bar (100 kPa).
 where solutions are involved, a concentration of 1 mol dm -3

Warning!  Standard pressure was originally defined as 1 atmosphere (101.325

kPa), and you will still find that in older books (including my calculations book). At
the time of writing (August 2010) there was at least one UK-based syllabus that
was still talking in terms of "1 atmosphere". It is essential to check your syllabus
to find out exactly what you need to learn.

Standard states

For a standard enthalpy change everything has to be present in its standard

state. That is the physical and chemical state that you would expect to find it in
under standard conditions.

That means that the standard state for water, for example, is liquid water, H 2O(l)
- not steam or water vapour or ice.

Oxygen's standard state is the gas, O2(g) - not liquid oxygen or oxygen atoms.

For elements which have allotropes (two different forms of the element in the
same physical state), the standard state is the most energetically stable of the
allotropes.

For example, carbon exists in the solid state as both diamond and graphite.
Graphite is energetically slightly more stable than diamond, and so graphite is
taken as the standard state of carbon.

Similarly, under standard conditions, oxygen can exist as O 2 (simply called

oxygen) or as O3 (called ozone - but it is just an allotrope of oxygen). The O 2
form is far more energetically stable than O 3, so the standard state for oxygen is
the common O2(g).

The symbol for standard enthalpy changes

The symbol for a standard enthalpy change is ΔH°, read as "delta H standard"
or, perhaps more commonly, as "delta H nought".

Note:  Technically, the "o" in the symbol should have a horizontal line through it,
extending out at each side. This is such a bother to produce convincingly without
the risk of different computers producing unreliable results, that I shall use the
common practice of simplifying it to "o".

Standard enthalpy change of reaction, ΔH°r

Remember that an enthalpy change is the heat evolved or absorbed when a

reaction takes place at constant pressure.

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.
That needs exploring a bit.

Here is a simple reaction between hydrogen and oxygen to make water:

 First, notice that the symbol for a standard enthalpy change of reaction is
ΔH°r. For enthalpy changes of reaction, the "r" (for reaction) is often
missed off - it is just assumed.
 The "kJ mol-1" (kilojoules per mole) doesn't refer to any particular
substance in the equation. Instead it refers to the quantities of all the
substances given in the equation. In this case, 572 kJ of heat is evolved
when 2 moles of hydrogen gas react with 1 mole of oxygen gas to form 2
moles of liquid water.
 Notice that everything is in its standard state. In particular, the water has
to be formed as a liquid.
 And there is a hidden problem! The figure quoted is for the reaction under
standard conditions, but hydrogen and oxygen don't react under standard
conditions.

Whenever a standard enthalpy change is quoted, standard conditions are

assumed. If the reaction has to be done under different conditions, a
different enthalpy change would be recorded. That has to be calculated
back to what it would be under standard conditions. Fortunately, you don't
have to know how to do that at this level.

Some important types of enthalpy change

Standard enthalpy change of formation, ΔH°f

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.

Note:  When you are trying to learn these definitions, you can make life easier for
yourself by picking out the key bit, and adding the other bits on afterwards. The
key bit about this definition is that you are forming 1 mole of a compound from its
elements. All the stuff about enthalpy change and standard conditions and
standard states is common to most of these definitions.

The equation showing the standard enthalpy change of formation for water is:

When you are writing one of these equations for enthalpy change of formation,
you must end up with 1 mole of the compound. If that needs you to write
fractions on the left-hand side of the equation, that is OK. (In fact, it is not just
OK, it is essential, because otherwise you will end up with more than 1 mole of
compound, or else the equation won't balance!)

The equation shows that 286 kJ of heat energy is given out when 1 mole of liquid
water is formed from its elements under standard conditions.

Standard enthalpy changes of formation can be written for any compound, even
if you can't make it directly from the elements. For example, the standard
enthalpy change of formation for liquid benzene is +49 kJ mol -1. The equation is:

If carbon won't react with hydrogen to make benzene, what is the point of this,
and how does anybody know what the enthalpy change is?

What the figure of +49 shows is the relative positions of benzene and its
elements on an energy diagram:

How do we know this if the reaction doesn't happen? It is actually very simple to
calculate it from other values which we can measure - for example, from
enthalpy changes of combustion (coming up next). We will come back to this
again when we look at calculations on another page.

Knowing the enthalpy changes of formation of compounds enables you to

calculate the enthalpy changes in a whole host of reactions and, again, we will
explore that in a bit more detail on another page.

And one final comment about enthalpy changes of formation:

The standard enthalpy change of formation of an element in its standard state is

zero. That's an important fact. The reason is obvious . . .

For example, if you "make" one mole of hydrogen gas starting from one mole of
hydrogen gas you aren't changing it in any way, so you wouldn't expect any
enthalpy change. That is equally true of any other element. The enthalpy change
of formation of any element has to be zero because of the way enthalpy change
of formation is defined.

Note:  Some sources say that the enthalpy change of formation of elements is
taken as zero by convention. That is simply nonsense! The standard enthalpy
change of formation of elements is zero because of the way the enthalpy change
is defined.
If this confuses you, ignore it!

Standard enthalpy change of combustion, ΔH°c

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.
The enthalpy change of combustion will always have a negative value, of course,
because burning always releases heat.

Two examples:

Notice:

 Enthalpy of combustion equations will often contain fractions, because

you must start with only 1 mole of whatever you are burning.
 If you are talking about standard enthalpy changes of combustion,
everything must be in its standard state. One important result of this is
that any water you write amongst the products must be there as liquid
water.

Similarly, if you are burning something like ethanol, which is a liquid under
standard conditions, you must show it as a liquid in any equation you use.

 Notice also that the equation and amount of heat evolved in the hydrogen
case is exactly the same as you have already come across further up the
page. At that time, it was illustrating the enthalpy of formation of water.
That can happen in some simple cases. Talking about the enthalpy
change of formation of water is exactly the same as talking about the
enthalpy change of combustion of hydrogen.

Questions to test your understanding

If this is the first set of questions you have done, please read the introductory page before you
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