Key points

Water can undergo autoionization to form H3 O+ and OH− ions. ​

The equilibrium constant for the autoionization of water, Kw , is 10−14 at​

25 ∘ C.

In a neutral solution, [H3 O+ ] = [OH− ]

​

In an acidic solution, [H3 O+ ] > [OH− ]

​

In a basic solution, [OH− ] > [H3 O+ ] ​

For aqueous solutions at 25 ∘ C, the following relationships are always true:

Kw = [H3 O+ ][OH− ] = 10−14

​ ​

pH + pOH = 14

+ −
The contribution of the autoionization of water to [H3 O ] and [OH​ ]
becomes significant for extremely dilute acid and base solutions.

Water is amphoteric
Water is one of the most common solvents for acid-base reactions. As we
discussed in a previous article on Brønsted-Lowry acids and bases, water is also
amphoteric, capable of acting as either a Brønsted-Lowry acid or base.

Practice 1: Identifying the role of water in a

reaction
In the following reactions, identify if water is playing the role of an acid, a
base, or neither.

Reaction Role of water

CH3 NH2 (aq) + H2 O(l) ⇌ CH3 NH+

​ ​ ​
−
3 (aq) + OH (aq)
​ ​
base 

HSO− ​
2−
​
+
4 (aq) + H2 O(l) ⇌ SO4 (aq) + H3 O (aq) ​ ​
acid
 2+
Cu2+ (aq) + 6 H2 O(l) → Cu(H2 O)6 (aq)
​ ​ ​ neither

Check

[Hide hint 1]

When water donates H+ to form OH− , it is acting as a Bronsted-Lowry acid.

When water accepts a proton for form H3 O+ , it is acting as a Bronsted-Lowry
​

base.

[Hide hint 2]

The correct answers are:

Autoionization of water
Since acids and bases react with each other, this implies that water can react
with itself! While that might sound strange, it does happen−water molecules
exchange protons with one another to a very small extent. We call this process
the autoionization, or self-ionization, of water.

The proton exchange can be written as the following balanced equation:

 H2 O(l) + H2 O(l) ⇌ H3 O+ (aq) + OH− (aq)

​ ​ ​

One water molecule donates a proton (orange sphere) to a neighboring water

molecule, which acts as a Bronsted-Lowry base by accepting that proton. The
products of the reversible acid-base reaction are hydronium and hydroxide.
One water molecule is donating a proton and acting as a Bronsted-Lowry acid,
while another water molecule accepts the proton, acting as a Bronsted-Lowry
base. This results in the formation of hydronium and hydroxide ions in a 1 : 1
molar ratio. For any sample of pure water, the molar concentrations of
hydronium, H3 O+ , and hydroxide, OH− , must be equal:
​

[H3 O+ ] = [OH− ]  in pure water

​

[Hide explanation]

Excellent question! Pure water means water with no other compounds

dissolved in the water. Pure water must also be degassed to remove dissolved
gases such as carbon dioxide, CO2 . This is because when carbon dioxide
​

dissolves in water, it can form small amounts of the weak acid carbonic acid,
H2 CO3 .
​ ​

Note that this process is readily reversible. Because water is a weak acid and a
weak base, the hydronium and hydroxide ions exist in very, very small
concentrations relative to that of non-ionized water. Just how small are these
concentrations? Let's find out by examining the equilibrium constant for this
reaction (also called the autoionization constant), which has the special symbol
Kw . ​

The autoionization constant, Kw ​

The expression for the autoionization constant is

Kw = [H3 O+ ][OH− ]
​ ​
(Eq. 1)

Remember that when writing equilibrium expressions, the concentrations of

solids and liquids are not included. Therefore, our expression for Kw does not
​

include the concentration of water, which is a pure liquid.

We can calculate the value of Kw at 25 ∘ C using [H3 O+ ], which is related to the

​ ​

pH of water. At 25 ∘ C, the pH of pure water is 7. Therefore, we can calculate the

concentration of hydronium ions in pure water:

[H3 O+ ] = 10−pH = 10−7  M  at 25 ∘ C

​

In the last section, we saw that hydronium and hydroxide form in a 1 : 1 molar
ratio during the autoionization of pure water. We can use that relationship to
calculate the concentration of hydroxide in pure water at 25∘ C:

[OH− ] = [H3 O+ ] = 10−7  M  at 25 ∘ C

​
This is a little tough to visualize, but 10−7 is an extremely small number! Within
a sample of water, only a small fraction of the water molecules will be in the
ionized form.

Now that we know [OH− ] and [H3 O+ ], we can use these values in our
​

equilibrium expression to calculate Kw at 25∘ C:

​

Kw = (10−7 ) × (10−7 ) = 10−14   at 25 ∘ C

​

Concept check: How many hydroxide and hydronium ions are in one liter of
water at 25∘ C?

[Hide the answer]

We know that at 25∘ C, the following relationship is true:

mol
[OH− ] = [H3 O+ ] = 10−7
L
​ ​

That means one liter of water contains 10−7 mol each of hydronium ions and
hydroxide ions. We can convert from moles to the number of ions using
Avogadro's number:

6.022 × 1023 ions

10−7 mol × = 6.022 × 1016 ions
1 mol
​

This sounds like a huge number! To put this in perspective, we can compare the
number of hydronium and hydroxide to the number of water molecules in the
same volume. There are 3.34 × 1025 molecules of water in one liter of water.
That is nearly 109 larger than the number of H3 O+ and OH− ions in solution!
​

Relationship between the autoionization constant,

pH, and pOH
The fact that Kw is equal to 10−14 at 25 ∘ C leads to an interesting and useful new
​

equation. If we take the negative logarithm of both sides of Eq. 1 in the previous
section, we get the following:
− log Kw = − log([H3 O+ ][OH− ])
​ ​

= −( log[H3 O+ ] + log[OH− ])
​

​ ​

+ −
= − log[H3 O ] + (− log[OH ])
​

= pH + pOH

[Hide explanation]

No worries! There are a just few rules you will want to remember for problems
in chemistry involving concepts like pH. For a review of useful rules for
logarithm calculations, see Sal's video on properties of logarithms.

We can abbreviate − log Kw as pKw , which is equal to 14 at 25 ∘ C:

​ ​

pKw = pH + pOH = 14  at 25 ∘ C

​
(Eq. 2)

Therefore, the sum of pH and pOH will always be 14 for any aqueous solution at
25 ∘ C. Keep in mind that this relationship will not hold true at other
temperatures, because Kw is temperature dependent! ​

−
Example 1: Calculating [OH ] from pH
An aqueous solution has a pH of 10 at 25 ∘ C.

What is the concentration of hydroxide ions in the solution?

Method 1: Using Eq. 1

One way to solve this problem is to first find [H+ ] from the pH:

[H3 O+ ] = 10−pH
​

​ ​

−10
= 10 M

We can then calculate [OH− ] using Eq. 1:

 Kw = [H3 O+ ][OH− ]   
​ ​ Rearrange to solve for [OH− ]

Kw
[OH− ] = Plug in values for Kw and [H3 O+ ]
​

[H3 O+ ]
​ ​ ​

​ ​

10−14
=
10−10
​

= 10−4  M

Method 2: Using Eq. 2

Another way to calculate [OH− ] is to calculate it from the pOH of the solution.
We can use Eq. 2 to calculate the pOH of our solution from the pH. Rearranging
Eq. 2 and solving for the pOH, we get:

pOH = 14 − pH

​
= 14 − 10 ​

=4

We can now use the equation for pOH to solve for [OH− ].

[OH− ] = 10−pOH
​ ​

−4
= 10  M

Using either method of solving the problem, the hydroxide concentration is

10−4  M for an aqueous solution with a pH of 10 at 25 ∘ C.

Definitions of acidic, basic, and neutral solutions

We have seen that the concentrations of H3 O+ and OH− are equal in pure
​

water, and both have a value of 10−7  M at 25 ∘ C. When the concentrations of

hydronium and hydroxide are equal, we say that the solution is neutral. Aqueous
solutions can also be acidic or basic depending on the relative concentrations of
H3 O+ and OH− .
​

In a neutral solution, [H3 O+ ] = [OH− ] ​

In an acidic solution, [H3 O+ ] > [OH− ] ​

 In a basic solution, [OH− ] > [H3 O+ ]
​

Practice 2: Calculating pH of water at 0 ∘ C

If the pKw of a sample of pure water at 0 ∘ C is 14.9, what is the pH of pure

​

water at this temperature?

Choose 1 answer:

A 7.90

B 7.00

C 6.00

D 7.45

Check

[Hide hint 1]

For aqueous solutions at 0 ∘ C

pKw = 14.9 = pH + pOH

[Hide hint 2]

Since pure water at 0 ∘ C is neutral, we know that [H3 O+ ] = [OH− ] and

​

pH = pOH.

If we plug this relationship into the equation for pKw , we get:

​

pH + pH = 14.9 = 2 × pH

14.9
​ ​

pH = = 7.45
2
​

The pH of pure water at at 0 ∘ C is 7.45.

Practice 3: Calculating pKw at 40 ∘ C ​

 The pH of pure water at 40 ∘ C is measured to be 6.75.

Based on this information, what is the pKw of water at 40 ∘ C?

​

Choose 1 answer:

A 13.5

B 14.5

C 14.0

D 13.8

Check

[Hide hint 1]

Pure water is neutral, so we know that [H3 O+ ] = [OH− ].

​

If we take the −log of both sides of the equation, we get

pH = pOH

[Hide hint 2]

We can find the relationship between pH and pKw for pure water at 40 ∘ C
​

using Eq. 2:

pKw = pH + pOH
​

= 2 × pH
​ ​

= 2 × 6.75

= 13.5

The pKw for pure water at 40 ∘ C is 13.5.

​

Autoionization and Le Chatelier's principle

We also know that in pure water, the concentrations of hydroxide and
hydronium are equal. Most of the time, however, we are interested in studying
aqueous solutions containing other acids and bases. In that case, what happens
to [H3 O+ ] and [OH− ]?
​

The moment we dissolve other acids or bases in water, we change [H3 O+ ]​

and/or [OH− ] such that the product of the concentrations is no longer is equal
to Kw . That means the reaction is no longer at equilibrium. In response, Le
​

Chatelier's principle tells us that the reaction will shift to counteract the change
in concentration and establish a new equilibrium.

For example, what if we add an acid to pure water? While pure water at 25 ∘ C
has a hydronium ion concentration of 10−7 M, the added acid increases the
concentration of H3 O+ . In order to get back to equilibrium, the reaction will
​

favor the reverse reaction to use up some of the extra H3 O+ . This causes the
​

concentration of OH to decrease until the product of [H3 O+ ] and [OH− ] is

−
​

once again equal to 10−14 .

Once the reaction reaches its new equilibrium state, we know that:

[H+ ] > [OH− ] because the added acid increased [H+ ]. Thus, our solution is
acidic!

[OH− ] < 10−7 M because favoring the reverse reaction decreased [OH− ] to
get back to equilibrium.

The important thing to remember is that any aqueous acid-base reaction can be
described as shifting the equilibrium concentrations for the autoionization of
water. This is really useful, because that means we can apply Eq. 1 and Eq. 2 to
all aqueous acid-base reactions, not just pure water!

Autoionization matters for very dilute acid and

base solutions
The autoionization of water is usually introduced when first learning about
acids and bases, and it is used to derive some extremely useful equations that
we've discussed in this article. However, we will often calculate [H+ ] and pH for
aqueous solutions without including the contribution from the autoionization
of water. The reason we can do this is because autoionization usually
contributes relatively few ions to the overall [H+ ] or [OH− ] compared to the
ions from additional acid or base.

The only situation when we need to remember the autoionization of water is

when the concentration of our acid or base is extremely dilute. In practice, this
means that we need to include the contribution from autoionization when the
concentration of H+ or OH− is within ~2 orders of magnitude (or less than) of
10−7 M. We will now go through an example of how to calculate the pH of a very
dilute acid solution.

Example 2: Calculating the pH of a very dilute acid

solution
Let's calculate the pH of a 6.3 × 10−8 M HCl solution. HCl completely
dissociates in water, so the concentration of hydronium ions in solution due to
HCl is also 6.3 × 10−8 M.

Try 1: Ignoring the autoionization of water

If we ignore the autoionization of water and simply use the formula for pH, we
get:

pH = −log[H+ ]

​
= −log[6.3 × 10−8 ] ​

= 7.20

Easy! We have an aqueous acid solution with a pH that is greater than 7. But,
wait, wouldn't that make it a basic solution? That can't be right!

Try 2: Including the contribution from autoionization to

[H+ ]
Since the concentration of this solution is extremely dilute, the concentration
of the hydronium from the hydrochloric acid is close to the [H+ ] contribution
from the autoionization of water. That means:

We have to include the contribution from autoionization to [H+ ]

Since the autoionization of water is an equilibrium reaction, we must solve

for the overall [H+ ] using the expression for Kw :
​

Kw = [H+ ][OH− ] = 1.0 × 10−14

​

If we say that x is the contribution of autoionization to the equilibrium

concentration of H+ and OH− , the concentrations at equilibrium will be as
follows:

[H+ ] = 6.3 × 10−8 M + x

[OH− ] = x

Plugging these concentrations into our equilibrium expression, we get:

Kw = (6.3 × 10−8 M + x)x = 1.0 × 10−14

​

​ ​

2 −8
= x + 6.3 × 10 x

Rearranging this expression so that everything is equal to 0 gives the following

quadratic equation:

0 = x2 + 6.3 × 10−8 x − 1.0 × 10−14

We can solve for x using the quadratic formula, which gives the following
solutions:

x = 7.3 × 10−8 M, −1.4 × 10−7 M

Since the concentration of OH− can't be negative, we can eliminate the second
solution. If we plug in the first value of x to get the equilibrium concentration of
H+ and calculate pH, we get:

pH = −log[H+ ]

= −log[6.3 × 10−8 + x]

​
= −log[6.3 × 10−8 + 7.3 × 10−8 ] ​

= −log[1.36 × 10−7 ]

= 6.87

Thus we can see that once we include the autoionization of water, our very
dilute HCl solution has a pH that is weakly acidic. Whew!

Summary
Water can undergo autoionization to form H3 O+ and OH− ions.
​

The equilibrium constant for the autoionization of water, Kw , is 10−14 at

​

25 ∘ C.
 In a neutral solution, [H3 O+ ] = [OH− ]
​

In an acidic solution, [H3 O+ ] > [OH− ]

​

In a basic solution, [OH− ] > [H3 O+ ]

​

For aqueous solutions at 25 ∘ C, the following relationships are always true:

Kw = [H3 O+ ][OH− ] = 10−14

​ ​

pH + pOH = 14

+ −
The contribution of the autoionization of water to [H3 O ] and [OH
​ ]
becomes significant for extremely dilute acid and base solutions.

[Attributions and references]