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Acids, bases and buffers calculations

The basics
[H+] = the concentration of protons
[HA] = concentration of the acid
[A-] = concentration of the conjugate base

You will either be ending you calculations with this:


pH = -log[H+]
Or starting them with this:
[H+] = 10-pH
Remember pH should always be given to 2 decimal places

pH calculations can be confusing because it often looks like you're not given all the
information you need. The reason for this is that we make a lot of assumptions about
the behaviour of acids and bases. These are in pink in this document). Learn these
and you won't struggle.

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Calculations for strong Acids


Assumption:
Strong acids fully dissociate in aqueous solution.
e.g. HCl H+ + ClThis means that [H+] = [HA]

How to calculate pH of a monobasic/monoprotic strong acid:


You will be given [HA]
pH = -log[HA]

To calculate [HA] of a strong acid:


You will be given pH
[HA] = 10-pH

How to calculate the pH of a diprotic/dibasic strong acid:


The acids still fully dissociate but the mole ratio is 1 HA : 2 H +
For example: H2SO4 2H+ + SO42Therefore the calculation you need to do is:
1. [H+] = 2 x [HA]
2. pH = -log[H+]

How to calculate [HA] of diprotic/dibasic strong acid:


1. [H+] = 10-pH
2. [HA] = [H+]/2
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Calculations for weak acids

Assumption:
Weak acids do not fully dissociate in solution.
This means that [H+] DOES NOT = [HA]
So pH cannot be calculated in the same way as for strong acids.

Weak acids dissociate in an equilibrium reaction.


e.g. CH3COOH CH3COO- + H+
Ka is the acid dissociation constant and the Ka equation describes this dissociation:
Ka = [H+][A-]
[HA]
(if you are asked for the expression for Ka this is the one to give. We will be using a
simplified version of it in the calculations but the simplified version isn't enough for
the marks.)

The bigger Ka the more dissociated the acid is.

The dissociation of acids is an endothermic process so Ka increases with


temperature.

How to calculate Ka
You will be given [H+] and [HA]
You will not be given [A-] for weak acid calculations.
There is an assumption that explains this:
For weak acids [H+] = [A-]
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This is because they are both produced by the dissociation of the acid and they are
formed in a 1:1 ratio and you don't need [A -]

The Ka equation can therefore be simplified to:


Ka = [H+]2
[HA]

This simplified equation can be used to calculate Ka but remember never to


give this as the expression for Ka in a stand-alone question.
This equation uses another important assumption:
You will have probably noticed that Ka is basically the same equation as Kc
(i.e. products/reactants). In Kc calculations we have to use the equilibrium
concentrations for everything. But for calculations involving Ka we can use the
initial concentration of Ka (i.e. the concentration you are given). This is
because the dissociation is extremely small.
Remember this assumption:
[HA] after dissociation = initial [HA]

How to calculate the pH of weak acids


We will also use the Ka equation for this but it will need to be rearranged to
make [H+] the subject. You will be given Ka and [HA]:
1. [H+] = ka[HA]
2. pH = -log[H+]

How to calculate the concentration of weak acids


We will also use the Ka equation for this but it will need to be rearranged to make
[HA] the subject. You will be given pH and Ka:
1. [H+] = 10-pH
2. [HA] = [H+]2/Ka

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pKa
pKa is related to ka in the same way that pH is related to [H+]

pka = -logKa
ka = 10-pKa

Calculations involving pKa


You might just be asked to calculate the pKa of a weak acid. In this case just
calculate Ka as normal and then do pka = -logKa.
Another possibility is that you will be given pKa instead of pH doing a weak acid or
buffer calculation.
All you need to do in this case is do ka = 10-pKa and then do the rest of the
calculation as normal.

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Calculations for bases


Remember: pH = log[H+]
This still applies to bases, though bases do not dissociate to release protons.
Bases accept protons from water so if we want to calculate the pH of a base we
need to find out the concentration of protons left in the water after the base has been
added.
To do this we need to use Kw (the ionic product of water)
Kw = [H+][OH-]
Pure water dissociates to produce [H+] and [OH-]:
H2O <--> H+ + OH-

At room temperature (298K) the pH of pure water is 7. This means that [H +] of


pure water is 1.0 x 10-7 (because [H]+ = 10-pH) and [OH-] is therefore also 1.0 x
10-7 because H2O dissociates in a 1:1 ratio.
This means that at room temperature Kw = [10-7][10-7] = 1.0 x 10-14 mol2 dm-6
Kw is dependent on temperature as the temperature increases the value of
Kw increases. So if you are doing calculations involving a temperature other
than 298K you will be given/asked to calculate a different Kw.

Assumption for base calculations:


Strong bases fully dissociate in aqueous solution.

e.g. NaOH Na+ + OHSo [OH-] = concentration of the base.


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But watch out for the mole ratio:


e.g. Ca(OH)2 Ca2+ + 2OHIn this case [OH-] = 2 x the concentration of the base.

How to calculate the pH of a strong base:


You will be given the concentration of the base. You may be given Kw (if not just use
1.0 x 10-14 mol2 dm-6).
Use the Kw equation but rearrange it to make [H +] the subject:
1. [H+] = Kw/[OH-]
(where [OH-] the concentration of the base. Remember to watch out for the mole
ratio see the assumptions above)
2. pH = -log[H+]

To calculate the concentration of a base:


You will be given pH. You may be given Kw (if not just use 1.0 x 10 -14 mol2 dm-6).
1. [H+] = 10-pH.
Use the Kw equation but rearrange it to make [OH-] the subject
2. [OH-] = Kw/[H+]

If your base is the type that dissociates to give 1 OH - you're done but if your base
dissociates to give 2 OH- (like Mg(OH)2) you need to do 2 x [OH-] to get the
concentration of the base (see the assumption above).

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Other calculations involving Ka


You may be asked to work out the pH of a solution of pure water. You might think
that the pH of pure water should always be 7 but this is only the case at a
temperature of 298K.
The pH of pure water depends on the concentration of H +, as usual. The
concentration of H+ depends on how dissociated the water is. The dissociation of
water is an endothermic process so the higher the temperature the more dissociated
the water, the higher the H+ and the lower the pH.

How to calculate the pH of pure water


Assumption:
In pure water [H+] = [OH-]
You will be given the relevant Kw for the particular temperature.
1. Use the Kw equation Kw = [H+][OH-]
2. Because [H+] = [OH-] we can find [H+] by doing
[H+] = Kw
3. Do pH = -log[H+]

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Buffers

Acidic buffers
A buffer solution is a mixture weak acid and its conjugate base.
The conjugate base is provided by a salt of the weak acid.
e.g. a buffer solution might be made from ethanoic acid and sodium ethanoate.

The composition of acidic buffers


The weak acid will not be fully dissociated in solution:
[HA] [H+] + [A-]
So the acid will provide lots of undissociated HA, a little A - and a little H+

The salt will be fully dissociated in solution:


NaA Na + AThe salt will therefore provide lots of A- (and some Na+/K+/random metal ion, which
we are not interested in)

Overall, the buffer contains:

Lots of HA

Lots of A-

A bit of H+

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You need to know how buffers work. We will look at this in a few pages time.

Standard buffer calculations

All buffer calculations use the Ka equation that you learned for weak acids:

Ka = [H+][A-]
[HA]

Assumption:
In a buffer mixture [H+] DOES NOT EQUAL [A-]. This is because the Acomes from both the weak acid and the salt. You will be given the
concentration (or mass - I will tell you what to do in each case) which
represents the A-.

Not sure which is [HA]? It's the one that you have a Ka for.
E.g. NH4Cl doesn't look like an acid, but it is and it ca 1n be used to make a buffer. In
this case you would be a given a Ka for [NH4+]

How to calculate the pH of a buffer solution


You will most likely be given [HA] and the concentration of the salt (this is [A -]) and
Ka.
1

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1. Calculate [H+]. You will need to rearrange the Ka equation to make [H +] the
subject:
[H+] = ka[HA]
[A-]
2. Do pH = -log[H+]

If you are given the mass of the salt: You need to convert this to concentration by
doing moles = mass/Mr then doing concentration = moles/volume(in dm 3). You won't
have a volume for the salt so use the volume of the acid as you are dissolving the
salt in the acid.
To calculate the concentration of [HA]
You will be given: pH, Ka and [A-]
1.do [H+] = 10-pH
2. Then rearrange the Ka equation to make [HA] the subject and use it to calculate
[HA]:
[HA] = [H+][A-]
Ka

How to calculate the concentration of [A-]


You will be given: pH, Ka and [HA]
1. do [H+] = 10-pH
2. Then rearrange the Ka equation to make [HA] the subject and use it to calculate
[A-]:
[A-] = Ka[HA]
[H+]

How to calculate the mass of [A-]


You will be given: pH, Ka and [HA]

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1. do [H+] = 10-pH
2. Then rearrange the Ka equation to make [HA] the subject and use it to calculate
[A-]:
[A-] = Ka[HA]
[H+]
3. Calculate the moles of A- by doing moles = concentration x volume(in dm 3).
(This volume will most likely be the volume of the acid, since A- will be a solid that
you are adding to the acid.)
4. Calculate the mass by doing moles x Mr of the salt.

Calculations for buffers made from a weak acid and


sodium Hydroxide

If you add NaOH to a weak acid they will react to make the salt. But, the acid needs
to be in EXCESS otherwise you will just have load of salt and water, not a buffer.
Example: CH3COOH + NaOH CH3COONa + H2O

How to calculate the pH of a buffer made from a weak acid and NaOH

You will be given: Ka, [HA] and volume of the weak acid, EITHER the concentration
and volume of NaOH or mass of NaOH.
This calculation is quite long so just follow the steps:
1. Calculate the moles of the weak acid: moles = concentration x volume
2. Calculate the moles of the NaOH: EITHER moles = concentration x volume
or moles = mass/Mr
3. Calculate the excess moles of the acid:
excess moles HA = moles of HA moles of NaOH
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4. Deduce the moles of the salt (the A-): Moles of NaOH = moles of A5. You can now calculate [H+] by using the Ka equation:
[H+] = ka[HA]
[A-]
Where [HA] is the moles of the weak acid and [A-] is the moles of the salt.
6. Get the pH by doing pH = -log[H+]

IMPORTANT: Remember [HA] and [A-] are, strictly speaking, concentrations


but in this example we have used moles instead of concentration. This is
because the units of [HA] and [A-] cancel out anyway, so when we use the Ka
equation we don't need to bother converting to volume.

Other calculations where NaOH is used to make a buffer:


How to calculate the concentration of NaOH needed to make a buffer of a particular
pH:
The concentration of A- is the same as the concentration of NaOH so you just need
to do exactly what you would do to calculate [A-]:
You will be given: pH, Ka and [HA]
1. do [H+] = 10-pH
2. Then rearrange the Ka equation to make [HA] the subject and use it to calculate
[A-]:
[A-] = Ka[HA]
[H+]

How to calculate the mass of NaOH


Again, you just need to do exactly what you would do to calculate the mass of A-,
since the moles of NaOH = moles of AYou will be given: pH, Ka and [HA]
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1. do [H+] = 10-pH
2. Then rearrange the Ka equation to make [HA] the subject and use it to calculate
[A-]:
[A-] = Ka[HA]
[H+]
3. Calculate the moles of A- by doing moles = concentration x volume(in dm 3).
(This volume will most likely be the volume of the acid, since A- will be a solid that
you are adding to the acid.)
4. Calculate the mass by doing moles x Mr of the salt.

More awkward buffer questions


You might be asked to calculate the pH of a buffer made from equal
concentrations/proportions of the acid and the salt. All you will be given is the Ka.

To calculate pH you would first need to get [H+] by using the Ka equation:
[H+] = ka[HA]
[A-]
But, as [HA] and [A-] are the equal, they will cancel out, leaving you with [H+] = ka.
Therefore to get you just need to do pH = -log Ka
You might also notice that in this situation the pH is equal to the pKa, since
pKa = -logKa. This observation is important.
How to calculate pH when you are given proportions of acid and salt, the ratio of
acid and salt etc.
For example: Calculate the pH of a buffer solution made from 2 parts Ethanoic acid
and 1 part Sodium Ethanoate. Ka = 1.7 x 10-5 mol dm-3.
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To calculate pH you would first need to get [H +] by using the Ka equation:


[H+] = ka[HA]
[A-]
All you have for [HA] and [A-] is the parts. These can be used instead of
concentrations as can ratios, proportions, anything else you are given for [HA] and
[A-]. This is because the units cancel out, so it doesn't matter if you use moles,
concentrations, whatever, in this equation.
So, for this example, you would do [H+] = 1.75 x 10-5 x [2]
[1]
Then do pH = -log[H+]

How to calculate the ratio of [A-] to [HA] needed to make a buffer solution of a
particular pH

You will be given: the pH and the Ka of the acid.


1. Work out [H+] by doing [H+] = 10-pH
Then you need to rearrange the Ka equation to make [A-]/[HA] the subject.
This leaves you with [A-]/[HA] = [H+]/Ka
So if you do [H+]/Ka the answer will the the ratio of [A-]:[HA]
For example: Calculate the ratio of Sodium ethanoate to ethanoic acid needed to
make a buffer solution of pH 4.63. Ka = 1.75 x 10 -5 mol dm-3
[H+] = 10-4.63 = 2.34 x 10-5
So [A-]/[HA] = 2.344 x 10-5/1.75 x 10-5
= 1.43
This is your ratio so this is your answer.
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You may also get asked to convert this ratio to concentrations. Remember with
decimal ratios, the number you get represents the variable on top of the division (in
this case the [A-] and the bottom of the division [HA] is 1 by default)
So the concentration of [A-] needs to be 1.43 mol dm-3 and the concentration of [HA]
will be 1 mol dm-3

Calculate changes to the pH when an acid or alkali is


added to a buffer solution.
To do these calculations you need to make sure you understand how buffers work.
The whole point of a buffer solution is to resist changes in pH so that the solution to
which the buffer is added will stay at around the characteristic pH of the buffer
solution.
The buffer keeps the pH roughly constant by mopping up any added protons
(to prevent a reduction in pH) and reacting with any base added (to prevent a
pH increase).

How it does it:


Remember Le Chateliers principle: If the conditions of a dyamic equilibrium are
changed the position of equilibrium will shift to oppose the change

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You buffer is made up of a weak acid and its salt, which can be described by this
equation:
[HA] <--> [H+] +[ A-]

If acid is added to a solution:


[H+] will increase. As there is lots of A- present, this can react with the H+ to reduce its
concentration. The H+ will therefore be removed from the solution and the pH will not
decrease.
What happens to the buffer:
The concentration of A- decreases
(all of the H+ will react with A- so A- will decrease by however many moles of H + you
added)
The concentration of HA increases, as the A- and H+ combine to make HA
(As the H+ and A- make the HA, the amount of HA will increase by however many
moles of H+ you added)

How to calculate changes to the pH if you add an acid.


1. Calculate the moles of the acid you are adding. You may actually be given the
moles but if not you will have to do moles = concentration x volume or moles =
mass/Mr depending on what you are given.
2. Calculated the moles of the weak acid that makes up the buffer and calculate the
moles of the salt. moles = concentration x volume
3. Remember, the moles of A- will decrease because it will react with the [H+] so you
need to calculate how many moles of [A-] are left by doing:
New moles of A- = initial moles of A- - moles of added acid
4. The moles of HA will increase as more is produced so you need to calculate how
many moles of HA you will end up with in total by doing:
New moles of HA = initial moles of HA + moles of added acid
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5. You can now calculate the new pH by using the Ka equation, rearranged to make
[H+] the subject:
[H+] = ka[H]
[A-]

6. Where Ka is the Ka of the weak acid that makes up the buffer, [HA] is the new
moles of HA and [A-] is the new moles of A-.
Then to calculate pH you will need to do pH = -log[H+]

If alkali is added to a solution


The added OH- will react with the H+ in the buffer. This decreases the concentration
of the H+. HA then dissociates to replace the lost H+ and the equilibrium position
shifts to the right and prevents a decrease in the pH. This also makes some more A What happens to the buffer:
The concentration of HA decreases
(by however many moles of alkali was added, since all the alkali will react)
The concentration of A- increases
(by however many moles of alkali were added, since the alkali reacts with the HA to
produce A-)

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How to calculate changes to the pH if you add an alkali.


1. Calculate the moles of the alkali you are adding. You may actually be given
the moles but if not you will have to do moles = concentration x volume or
moles = mass/Mr depending on what you are given.
2. Calculated the moles of the weak acid that makes up the buffer and
calculate the moles of the salt.
3. Remember, the moles of A- will increase as more is formed when HA
dissociates so you need to work out how much A- you will end up with in total:
New moles of A- = initial moles of A- + moles of added acid
4. The moles of HA will decrease as it dissociates to replace the H + so you
need to find out how much you have left by doing
New moles of HA = initial moles of HA - moles of added acid
5. You can now calculate the new pH by using the Ka equation, rearranged to
make [H+] the subject
[H+] = ka[HA]
[A-]
Where Ka is the Ka of the weak acid that makes up the buffer, [HA] is the new moles
of HA and [A-] is the new moles of A-.
6. Then to calculate pH you will need to do pH = -log[H+]

Calculations involving neutralisation reactions


In this type of calculation you will be asked to work out the pH of the solution after a
strong acid is mixed with a base. How you will do this depends on whether the acid
or the base is in excess.

What you will be given:


[HA], the volume of the acid and either the concentration and volume of the base or
the mass of the base.

For monoprotic/monobasic acids (e.g HCl):


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1. Calculate the moles of both the acid and the alkali (moles = concentration x
volume or moles = mass/Mr)
2. Deduce which reagent is in excess. Whichever has the greatest number of moles
is in excess. The other reagent is considered to be the limiting reagent.
3. Calculate the number of excess moles by doing:
excess moles = moles of excess reagent - moles of limiting reagent.
4. Convert the moles of the excess reagent to concentration by doing:
concentration = moles/total volume. (The total volume is the volume of the acid +
the volume of the base)
5. The next steps depend on whether the acid or base was in excess. If the acid
was the excess reagent, follow the steps for determining the pH of a strong acid. If
the base was in excess follow the steps for determining the pH of a base.

For diprotic/dibasic acids (e.g. H2SO4)

The steps above still apply but you have to be careful with the mole ratio - this will
make it harder to see which is in excess. This is the one that everyone struggles with
so I will show you a full worked example:

Example question: Calculate the pH when a 0.0200 dm3 of a 0.250 mol dm-3
solution of H2SO4 is mixed with 0.0200 cm3 of a 0.190 cm3 solution ok KOH.
H2SO4 + 2KOH --> K2SO4 + H2O
Following the steps in the previous example we need to calculate the moles of each
reagent first (using moles = concentration x volume):
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Moles of H2SO4 = 0.0200 x 0.250


= 0.005 moles
Moles of KOH = 0.0200 x 0.190
= 0.0038 moles
Then, we need to deduce which is in excess and by how much. This is where is is a
little bit more awkward than in it is for monoprotic acids. We can see that the H 2SO4
has the greater moles but the 1:2 molar ratio between the H 2SO4 and the KOH
means we cannot just do moles of H2SO4 - moles of KOH in order to find out the
excess moles.
This is what we need to do:
Even though there is a 1:2 molar ratio between the H2SO4 and the KOH the molar
ratio between H+ and OH- is still 1:1 (this is always the case in neutralisation
reactions). This is because the ionic equation for the reaction simplifies to H+ + OH--> H2O
So, we can determine the moles of H + and then compare that to the moles of KOH in
order to work out what is in excess.
H2SO4 is a strong acid so one mole of H2SO4 dissociates to give 2 moles of H+:
H2SO4 --> 2H+ + SO42We already know that the moles of H2SO4 is 0.005, so this means the moles of H+ is
0.01.
We can now follow the same steps as for a monoprotic acid, but we need to make
sure we use the moles of H+ rather than the moles of the acid. These are the steps:
1. Deduce which reagent is in excess. Whichever has the greatest number of moles
is in excess. The other reagent is considered to be the limiting reagent.
2. Calculate the number of excess moles by doing:
excess moles = moles of excess reagent - moles of limiting reagent.
3. Convert the moles of the excess reagent to concentration by doing:
concentration = moles/total volume. (The total volume is the volume of the acid +
the volume of the base)
4. The next steps depend on whether the acid or base was in excess. If the acid
was the excess reagent, follow the steps for determining the pH of a strong acid. If
the base was in excess follow the steps for determining the pH of a base.
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So, for our example: the excess moles will be the moles of H+ - moles of KOH
excess moles = 0.01 - 0.0038
= 0.0062 moles of H+
We now need to convert back to concentration. Remember that the volume needs to
be the total volume which in this case is 0.0200 + 0.0200 = 0.040 dm 3.
The concentration of H+ is therefore 0.0062/0.040 = 0.155 mol dm -3
Since the acid was in excess we can now just do pH= -log[H +]
= 0.81

To recap: the difference between this calculation and the monoprotic acid calculation
is that we need to calculate the moles of H+ (moles of acid x 2) and use this rather
than the concentration of the acid when we are working out the excess moles.

This is important: if you get a question which asks you to work out the pH
when a base is added to a weak acid you will probably find that the acid is in
excess and you need to treat it like a weak acid calculation. If you have a
reaction involving a weak acid and the base is in excess you can treat is as a
neutralisation calculation and follow these instructions.

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