8/16/2016 enthalpychangeofneutralisation

ENTHALPY CHANGE OF
NEUTRALISATION

This page looks briefly at enthalpy changes of neutralisation. In

common with my experience with most of the other pages in this

section, searches for reliable data throw up various values for

the same reaction. Don't worry too much about this. It doesn't

actually affect the arguments.

Enthalpy change of neutralisation

Defining standard enthalpy change of neutralisation

The standard enthalpy change of neutralisation is the

enthalpy change when solutions of an acid and an alkali

react together under standard conditions to produce 1

mole of water.

Notice that enthalpy change of neutralisation is always

measured per mole of water formed.

Enthalpy changes of neutralisation are always negative - heat is

given out when an acid and and alkali react. For reactions

involving strong acids and alkalis, the values are always very
-1
closely similar, with values between -57 and -58 kJ mol .

That varies slightly depending on the acid-alkali combination

(and also on what source you look it up in!).

Why do strong acids reacting with strong alkalis give closely

similar values?

We make the assumption that strong acids and strong alkalis

are fully ionised in solution, and that the ions behave

independently of each other. For example, dilute hydrochloric

acid contains hydrogen ions and chloride ions in solution.

Sodium hydroxide solution consists of sodium ions and

hydroxide ions in solution.

The equation for any strong acid being neutralised by a strong

alkali is essentially just a reaction between hydrogen ions and

hydroxide ions to make water. The other ions present (sodium

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and chloride, for example) are just spectator ions, taking no part

in the reaction.

The full equation for the reaction between hydrochloric acid and

sodium hydroxide solution is:

. . . but what is actually happening is:

If the reaction is the same in each case of a strong acid and a

strong alkali, it isn't surprising that the enthalpy change is

similar.

Note: Actually, of course, the enthalpy changes should be

the same, not similar, if the assumptions we are making are

exactly true! The small differences between strong acid-

strong base combinations are almost invariably glossed over

at this level. In fact, I can't remember ever seeing this

discussed in any source - textbook or web. It isn't uncommon

to find a list of enthalpy changes of neutralisation showing

some variability in the strong acid-strong alkali cases, and

then a few lines later on, this is ignored completely with a

statement that in these cases, the enthalpy changes of

neutralisation are the same, because . . .

I have decide not to waste time trying to sort out the exact

reasons for the problem, because I suspect it will take ages

and ages, and it is never going to get asked at this level

anyway.

Why do weak acids or weak alkalis give different values?

In a weak acid, such as ethanoic acid, at ordinary

concentrations, something like 99% of the acid isn't actually

ionised. That means that the enthalpy change of neutralisation

will include other enthalpy terms involved in ionising the acid as

well as the reaction between the hydrogen ions and hydroxide

ions.

And in a weak alkali like ammonia solution, the ammonia is also

present mainly as ammonia molecules in solution. Again, there

will be other enthalpy changes involved apart from the simple

formation of water from hydrogen ions and hydroxide ions.

For reactions involving ethanoic acid or ammonia, the measured

enthalpy change of neutralisation is a few kilojoules less

exothermic than with strong acids and bases.

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For example, one source which gives the enthalpy change of

neutralisation of sodium hydroxide solution with HCl as -57.9 kJ

-1 -1
mol , gives a value of -56.1 kJ mol for sodium hydroxide

solution being neutralised by ethanoic acid.

For very weak acids, like hydrogen cyanide solution, the

enthalpy change of neutralisation may be much less. A different

source gives the value for hydrogen cyanide solution being

-1
neutralised by potassium hydroxide solution as -11.7 kJ mol ,

for example.

Questions to test your understanding

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

introductory page before you start. You will need to use the BACK BUTTON

on your browser to come back here afterwards.

questions on neutralisation enthalpies

answers

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Jim Clark 2010 (modified July 2013)

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