If you're seeing this message, it means we're having trouble loading external resources on our website.

If you're behind a web filter, please make sure that the domains *.kastatic.org and *.kasandbox.org are unblocked.

Main content

Water autoionization and Kw

Autoionization of water, the autoionization constant Kw, and the relationship between [H⁺] and [OH⁻] in aqueous solutions. 

Key points

  • Water can undergo autoionization to form H3O+ and OH ions.
  • The equilibrium constant for the autoionization of water, Kw, is 1014 at 25C.
  • In a neutral solution, [H3O+]=[OH]
  • In an acidic solution, [H3O+]>[OH]
  • In a basic solution, [OH]>[H3O+]
  • For aqueous solutions at 25C, the following relationships are always true:
Kw=[H3O+][OH]=1014
pH+pOH=14
  • The contribution of the autoionization of water to [H3O+] 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.
1

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 happenwater 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:
 H2O(l)+H2O(l)H3O+(aq)+OH(aq)
space filling models to show two water molecules, where each water molecule is represented as a large red sphere (oxygen) stuck to two small grey sphere (hydrogen). The products are hydronium ion, which has 3 hydrogens and a positive charge, and hydroxide, which has one hydrogen and a negative charge.
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, H3O+, and hydroxide, OH, must be equal:
[H3O+]=[OH]  in pure water
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=[H3O+][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 25C using [H3O+], which is related to the pH of water. At 25C, the pH of pure water is 7. Therefore, we can calculate the concentration of hydronium ions in pure water:
[H3O+]=10pH=107 M  at 25C
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 25C:
[OH]=[H3O+]=107 M  at 25C
This is a little tough to visualize, but 107 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 [H3O+], we can use these values in our equilibrium expression to calculate Kw at 25C:
Kw=(107)×(107)=1014  at 25C
Concept check: How many hydroxide and hydronium ions are in one liter of water at 25C?

Relationship between the autoionization constant, pH, and pOH

The fact that Kw is equal to 1014 at 25C 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:
logKw=log([H3O+][OH])=(log[H3O+]+log[OH])=log[H3O+]+(log[OH])=pH+pOH
We can abbreviate logKw as pKw, which is equal to 14 at 25C:
pKw=pH+pOH=14  at 25C(Eq. 2)
Therefore, the sum of pH and pOH will always be 14 for any aqueous solution at 25C. 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 25C.
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:
[H3O+]=10pH=1010M
We can then calculate [OH] using Eq. 1:
Kw=[H3O+][OH]   Rearrange to solve for [OH][OH]=Kw[H3O+]Plug in values for Kwand [H3O+]=10141010=104 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=14pH=1410=4
We can now use the equation for pOH to solve for [OH].
[OH]=10pOH=104 M
Using either method of solving the problem, the hydroxide concentration is 104 M for an aqueous solution with a pH of 10 at 25C.

Definitions of acidic, basic, and neutral solutions

We have seen that the concentrations of H3O+ and OH are equal in pure water, and both have a value of 107 M at 25C. 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 H3O+ and OH.
  • In a neutral solution, [H3O+]=[OH]
  • In an acidic solution, [H3O+]>[OH]
  • In a basic solution, [OH]>[H3O+]

Practice 2: Calculating pH of water at 0C

If the pKw of a sample of pure water at 0C is 14.9, what is the pH of pure water at this temperature?
Choose 1 answer:

Practice 3: Calculating pKw at 40C

The pH of pure water at 40C is measured to be 6.75.
Based on this information, what is the pKw of water at 40C?
Choose 1 answer:

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 [H3O+] and [OH]?
The moment we dissolve other acids or bases in water, we change [H3O+] 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 25C has a hydronium ion concentration of 107M, the added acid increases the concentration of H3O+. In order to get back to equilibrium, the reaction will favor the reverse reaction to use up some of the extra H3O+. This causes the concentration of OH to decrease until the product of [H3O+] and [OH] is once again equal to 1014.
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]<107M 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 107M. 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 6.3×108M HCl solution. HCl completely dissociates in water, so the concentration of hydronium ions in solution due to HCl is also 6.3×108M.

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[6.3×108]=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]=1.0×1014
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+]=6.3×108M+x
[OH]=x
Plugging these concentrations into our equilibrium expression, we get:
Kw=(6.3×108M+x)x=1.0×1014=x2+6.3×108x
Rearranging this expression so that everything is equal to 0 gives the following quadratic equation:
0=x2+6.3×108x1.0×1014
We can solve for x using the quadratic formula, which gives the following solutions:
x=7.3×108M,1.4×107M
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[6.3×108+x]=log[6.3×108+7.3×108]=log[1.36×107]=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 H3O+ and OH ions.
  • The equilibrium constant for the autoionization of water, Kw, is 1014 at 25C.
  • In a neutral solution, [H3O+]=[OH]
  • In an acidic solution, [H3O+]>[OH]
  • In a basic solution, [OH]>[H3O+]
  • For aqueous solutions at 25C, the following relationships are always true:
Kw=[H3O+][OH]=1014
pH+pOH=14
  • The contribution of the autoionization of water to [H3O+] and [OH] becomes significant for extremely dilute acid and base solutions.

Want to join the conversation?

  • leaf green style avatar for user sarvin9574
    in Example 2 , i didn't understand why [H] = 6.3x10...+ x ,why was x added to the concentration of H what does it have to do with that ?
    (18 votes)
    Default Khan Academy avatar avatar for user
    • spunky sam blue style avatar for user Ernest Zinck
      The HCl is so dilute that we must consider both the concentration of H⁺ from the HCl and the concentration of H⁺ from the ionization of the water.
      [H⁺] from HCl = 6.3 × 10⁻⁸ mol/L
      [H⁺] from H₂O = x mol/L
      ∴ Total [H⁺] = (6.3 × 10⁻⁸ + x) mol/L
      (33 votes)
  • leafers seed style avatar for user Amit Mukherjee
    In this article, the value of Kw has been given as 10^-14. But should it not be 10^-14(mol/L)^2? Why have the units been dropped?
    (12 votes)
    Default Khan Academy avatar avatar for user
  • aqualine ultimate style avatar for user just_miku.py
    How come we multiply the pH value by 2 when the temperature is 0C°?
    (4 votes)
    Default Khan Academy avatar avatar for user
    • piceratops seed style avatar for user RogerP
      In pure water, at any temperature, [H3O+] equals [OH-].

      At 0 C, pKw = 14.9.

      pKw = pH + pOH. As [H3O+] equals [OH-], then pH must equal pOH because these are just the negative logs of the respective concentrations, which are equal.

      Therefore, the equation becomes pKw = pH + pH = 2 x pH. Therefore, pH = pKw/2.

      So the division by two has nothing to do with temperature. It is just because [H3O+] equals [OH-], which is the case at any temperature for pure water.
      (10 votes)
  • leafers seed style avatar for user Amit Mukherjee
    When an acid is added to pure water, the resultant solution will have more hydronium ions and fewer hydroxide ions. So, the new equilibrium could be something like [H3O+] = 10^-9 and [OH-] = 10^-5. Is this correct?
    (0 votes)
    Default Khan Academy avatar avatar for user
  • spunky sam blue style avatar for user Nasrullah Sami
    In exercise 2, the question states that the solution has a hydronium ion conc. of 6.3*10^-8 M. It doesn't specifically say that this measure excludes the number of H+ ions that come from water. Do we always have to assume that?
    (5 votes)
    Default Khan Academy avatar avatar for user
    • mr pants teal style avatar for user RolandKan3
      The article also left me wondering this. If someone states that "a HCl solution with a hydronium ion concentration of 6.3 * 10^-8 M" I would assume that the aqueous solution has the mentioned hydronium ion concentration and use that to calculate the pH. Shouldn't the creator of the article have seperately mentioned that the concentration excludes the H+ coming from autoionization of water. Or maybe I'm missing something? Idk.
      (3 votes)
  • male robot donald style avatar for user johnny
    I understand how adding an acid such as HCl to water increases the number of H30 ions as the released H+ attaches to H20, but I dont get it why should it decrease the number of OH in a way that keep the product of both constant. Say for the sake of easy math there was 1000 of each ion, the product of both would be 1 million. However, since there is aproximatly 560 million H20 for every 1 OH in neutral water, if I dump over 1 billion HCl molecules there should be about 1 billion more H30 ions and only about 2 fewer OH ions. and 1 billion and a thousand X 998 dosent make a million.
    (2 votes)
    Default Khan Academy avatar avatar for user
    • piceratops ultimate style avatar for user Nhi Tran
      you can use reaction equilibrium to explain this:
      at 25 degree Celsius, K(w)= 10^(-14)
      Let [H+] and [OH-] be the initial concentration of H+ and OH- in water
      Before adding acid: K(w) = [H+]*[OH-] = 10^(-14)
      After adding acid with x mol/l concentration of [H+]: Q(c) = {[H+] + x}*[OH-]
      Since {[H+] + x} > [H+] => {[H+] + x}*[OH-] > [H+]*[OH-] => Q(c) > K(w)
      According to Lechatelier's equilibrium law, the reaction must reach equilibrium by decreasing the new [H+] in the solution. To do this, it must use OH- to react with this newly added H+.
      As a result, after the reaction reaches equilibrium, both [H+] and [OH-] decreases.
      (4 votes)
  • blobby green style avatar for user Eyasu Kebede
    In this question: "Suppose a nanotechnological innovation allows every single charged ion to be precisely identified and removed from a small volume of water. Which of the following describes K_a for the water at the end of the process, assuming that the filtered water is given adequate time to re-equilibrate?"

    The answer was Ka = Kw = 10^-14. But, I thought Ka would equal 10^-7. Could you explain this?
    (3 votes)
    Default Khan Academy avatar avatar for user
  • piceratops ultimate style avatar for user wanglx123456789
    "Since the concentration of OH- can't be negative, we can eliminate the second solution.
    Doesn't it sound too loose and unlogical? We can just casually remove a certain value from calculation?
    (0 votes)
    Default Khan Academy avatar avatar for user
    • leaf red style avatar for user Richard
      If you're solving a quadratic equation, you can receive a maximum of two real solutions. In this case we get that with one being positive and one being negative. So it makes mathematical sense that we get two answers, but physically only the positive answer makes sense.

      A negative concentration means you have less than 0 moles of hydroxide, or less than nothing. We can have no hydroxide possible, 0 moles of hydroxide in the solution, but not less than that.

      It's similar to problems in geometry where we can only have positive areas or volumes since we're considering real physical objects even if the algebra sometimes allows a negative answer.

      Hope that helps.
      (7 votes)
  • leaf green style avatar for user Elliot Natanov
    We see that the pKa of water is 14 at 25 degrees Celsius, since the -log of 10^-14 is 14. However, my organic chemistry textbook says the pKa of water is 15.7 at 25 degrees Celsius. Can you please shed some light on this?
    (2 votes)
    Default Khan Academy avatar avatar for user
  • blobby green style avatar for user vitti
    Why don't we include solids/liquids in Kw calculations? Are we only including gasses then?
    (3 votes)
    Default Khan Academy avatar avatar for user