Chapter 9

Systematic Treatment of
Equilibrium

Charge Balance

Basic concept of electroneutrality

Sum of the positive charges in
solution equals the sum of the
negative charges in solution.

What are charged species?

Ions in solution.
What species will ionize?
Sodium Chloride (NaCl) will
dissolve into solution to give us
Na+ and Cl- in equal amounts.
Glucose will dissolve in solution but
not generate ions.

What do we get when we put

something like phosphoric acid into
solution.

H3PO4

It is time to recall some chemistry.

We know that PO43- will result but what else.

H+ to be sure.
Phosphate goes thru a series of equilibrium steps
to give a range of species

H2PO4- , HPO42- , PO43- that have charge.

Note: Species with alkali metal ions combined will

not really exist. (There will be no NaHPO4- for
example)

What Else

Since it is a water solution and we

know that water can dissociate
then we would have OH- also.
So we would have H+ for cations.
And OH-, H2PO4- , HPO42- , PO43- for
anions.

The Balanced Equation

cations = anions
Ions of charge greater than one must
be accounted for. So for example if
we have a calcium ion formed then
each calcium ion has a double charge
we must multiply the concentration of
such an ion by this charge.

Charge Balance

So for phosphoric acid we have the following

charge balance.

[H+] = [H2PO4-] + 2[HPO4=]+3[PO43-]+[OH-]

The H3PO4 that remains in solution has no

charge and need not be accounted for in the
charge balance.

Charge Balance

What if we put trisodium phosphate

into solution. Na3PO4

This is the salt of a strong base and

the sodium can be assumed to
completely dissociate. (We know
what ion pairs are and we will elect
to ignore them unless directed
otherwise.)

What ions will be have?

Well we will have Na+ and PO43-.

But!!!
Phosphate ion is a fairly strong base.
That is it would love the rob a proton
from somewhere and become HPO42This ion in turn is a relatively strong base
too and will steal another proton (H2PO4-)
This new ion is also capable of the next
step giving us H3PO4.

What ions/species will be have

So for this solution we will possibly

have.
PO43- , HPO42- , H2PO4- , H3PO4 and Na+
And the ions from water. H+ and OHSo our charge balance is
[H+] + [Na+] = [H2PO4-] + 2[HPO4=]+3[PO43-]+[OH-]

How much of each species will

there be?

If we were to put K2PO4 into

solution then what would we
expect to see for relative amount
of each of these species.

Warning

I do not want to see species like

NaPO42- cropping up in charge
balances. They do not exist! This
is usually a pit fall for you all in
preparing your charge balances.

Mass Balance

All this tells us that what be put into our

solution is in there someplace. This is our
statement of conservation of mass.

So if we put Phosphoric acid into solution it will

be in there as one of the phosphate species.
Phosphoric acid is an ingredient of diet pepsi.
We know that it undergoes these acid base
interactions so our Mass balance accounts for
that.

Mass Balance of Phosphoric Acid

CH3PO4 = [H3PO4] + [H2PO4-] + [HPO42-] + [PO43-]

This CH3PO4 is often referred to as the Formal

Concentration. So if we put 1.5 mmoles of
phosphoric acid into 0.50 liters of water then
this formal concentration would be 3.0 mM.

We must account for each species, charged or

not, and since we are looking at concentration
and not charge we should not multiply by the
charge in this case.

Mass Balance of Na3PO4

If we do not know the concentration we

can still use the mass balance.
When we put this salt into water we
know we get three sodium for each
phosphate. To set this up into an
equation we could write.
[Na+] = 3 * phosphate concentration
Have I written this backward?????

Mass Balance

So we would have a mass balance of

[Na+] = 3{[H3PO4] + [H2PO4-] + [HPO42-] +

[PO43-]}

Steps in solving such systems.

Write all pertinent reactions (dont forget

water)
Write the charge balance
Write the mass balances ( there might be
more than one )
Count the equations and unknowns. You
will need to have and equal number here.
Now just solve!

Solve?

Let us look at the trisodium phosphate.

Unknowns

Seven Unknown so we need seven equations.

[Na+] [H3PO4] [H2PO4-] [HPO42-] [PO43-] [H+] [OH-]

Mass balance on sodium ion
Mass balance on phosphate ions
Kw
Charge balance
Three acid equilibria

Full solution will be a seventh order polynomial.

Other systems

That was just a simple system

these equilibrium systems can
become very complex and solution
depends on our knowing all the
equilibria involved.

Example CaF2 Solubility

CaF2 Crystal Structure

CaF2 Solubility

Two equilibria involved

Ksp

Kb for F- once it is dissolved

Setting conditions can help solve

this problem

CaF2 Solubility

Acid Rain

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Acid Rain