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Weak acid-base equilibria

Weak acid and base ionization reactions and the related equilibrium constants,  Ka and Kb. Relating Ka and Kb to pH, and calculating percent dissociation. 

Key points:

  • For a generic monoprotic weak acid HA with conjugate base A, the equilibrium constant has the form:
Ka=[H3O+][A][HA]
  • The acid dissociation constant Ka quantifies the extent of dissociation of a weak acid. The larger the value of Ka, the stronger the acid, and vice versa.
  • For a generic weak base B with conjugate acid BH+, the equilibrium constant has the form:
Kb=[BH+][OH][B]
  • The base dissociation constant (or base ionization constant) Kb quantifies the extent of ionization of a weak base. The larger the value of Kb, the stronger the base, and vice versa.

Strong vs. weak acids and bases

Strong acids and strong bases refer to species that completely dissociate to form ions in solution. By contrast, weak acids and bases ionize only partially, and the ionization reaction is reversible. Thus, weak acid and base solutions contain multiple charged and uncharged species in dynamic equilibrium.
In this article, we will discuss acid and base dissociation reactions and the related equilibrium constants: Ka, the acid dissociation constant, and Kb, the base dissociation constant.

Warm-up: Comparing acid strength and pH

Problem 1: Weak vs. strong acids at the same concentration

We have two aqueous solutions: a 2.0M solution of hydrofluoric acid, HF(aq), and a 2.0M solution of hydrobromic acid, HBr(aq). Which solution has the lower pH?
Choose 1 answer:

Problem 2: Weak vs. strong acids at different concentrations

This time we have a 2.0M solution of hydrofluoric acid, HF(aq), and a 1.0M solution of hydrobromic acid, HBr(aq). Which solution has the lower pH?
Assume we don't know the equilibrium constant for the dissociation of hydrofluoric acid.
Choose 1 answer:

Weak acids and the acid dissociation constant, Ka

Weak acids are acids that don't completely dissociate in solution. In other words, a weak acid is any acid that is not a strong acid.
The strength of a weak acid depends on how much it dissociates: the more it dissociates, the stronger the acid. In order to quantify the relative strengths of weak acids, we can look at the acid dissociation constant Ka, the equilibrium constant for the acid dissociation reaction.
For a generic monoprotic weak acid HA, the dissociation reaction in water can be written as follows:
HA(aq)+H2O(l)H3O+(aq)+A(aq)
Based on this reaction, we can write our expression for equilibrium constant Ka:
Ka=[H3O+][A][HA]
The equilibrium expression is a ratio of products to reactants. The more HA dissociates into H+ and the conjugate base A, the stronger the acid, and the larger the value of Ka. Since pH is related to [H3O+], the pH of the solution will be a function of Ka as well as the concentration of the acid: the pH decreases as the concentration of the acid and/or Ka increase.

Common weak acids

Malic acid, C4H6O5, is an organic acid found in apples. Image from Wikimedia Commons, CC BY-SA 3.0.
Carboxylic acids are a common functional group in organic weak acids, and they have the formula COOH. Malic acid (C4H6O5), an organic acid that contains two carboxylic acid groups, contributes to the tart flavor of apples and some other fruits. Since there are two carboxylic acid groups in the molecule, malic acid can potentially donate up to two protons.
The table below lists some more examples of weak acids and their Ka values.
NameFormulaKa(25C)
AmmoniumNH4+5.6×1010
Chlorous acidHClO21.2×102
Hydrofluoric acidHF7.2×104
Acetic acidCH3COOH1.8×105
Concept check: Based on the table above, which is a stronger acidacetic acid or hydrofluoric acid?

Example 1: Calculating % dissociation of a weak acid

One way to quantify how much a weak acid has dissociated in solution is to calculate the percent dissociation. The percent dissociation for weak acid HA can be calculated as follows:
% dissociation=[A(aq)][HA(aq)]×100%
If nitrous acid (HNO2) has a Ka of 4.0×104 at 25C, what is the percent dissociation of nitrous acid in a 0.400 M solution?
Let's go through this example step-by-step!

Step 1: Write the balanced acid dissociation reaction

First, let's write the balanced dissociation reaction of HNO2 in water. Nitrous acid can donate a proton to water to form NO2(aq):
HNO2(aq)+H2O(l)H3O+(aq)+NO2(aq)

Step 2: Write the expression for Ka

From the equation in Step 1, we can write the Ka expression for nitrous acid:
Ka=[H3O+][NO2][HNO2]=4.0×104

Step 3: Find [H+] and [NO2] at equilibrium

Next, we can use an ICE table to determine algebraic expressions for the equilibrium concentrations in our Ka expression:
HNO2(aq)H3O+NO2
Initial0.400M00
Changex+x+x
Equilibrium0.400Mxxx
Plugging the equilibrium concentrations into our Ka expression, we get:
Ka=(x)(x)(0.400Mx)=4.0×104
Simplifying this expression, we get the following:
x20.400Mx=4.0×104
This is a quadratic equation that can be solved for x either by using the quadratic formula or an approximation method.
Either method will give x=0.0126 M. Therefore, [NO2]=[H3O+]=0.0126 M.

Step 4: Calculate percent dissociation

To calculate percent dissociation, we can use the equilibrium concentrations we found in Step 3:
% dissociation=[NO2][HNO2]=0.0126 M0.400 M×100%=3.2%
Therefore, 3.2% of the HNO2 in solution has dissociated into H+ and NO2 ions.

Weak bases and Kb

Let's now examine the base dissociation constant (also called the base ionization constant) Kb. We can start by writing the ionization reaction for a generic weak base B in water. In this reaction, the base accepts a proton from water to form hydroxide and the conjugate acid, BH+:
B(aq)+H2O(l)BH+(aq)+OH(aq)
We can write the expression for equilibrium constant Kb as follows:
Kb=[BH+][OH][B]
From this ratio, we can see that the more the base ionizes to form BH+, the stronger the base, and the larger the value of Kb. As such, the pH of the solution will be a function of both the value of Kb as well as the concentration of the base.

Example 2: Calculating the pH of a weak base solution

What is the pH of a 1.50 M solution of ammonia, NH3? (Kb=1.8×105)
This example is an equilibrium problem with one extra step: finding pH from [OH]. Let's go through the calculation step-by-step.

Step 1: Write the balanced ionization reaction

First, let's write out the base ionization reaction for ammonia. Ammonia will accept a proton from water to form ammonium, NH4+:
NH3(aq)+H2O(l)NH4+(aq)+OH(aq)

Step 2: Write the expression for Kb

From this balanced equation, we can write an expression for Kb:
Kb=[NH4+][OH][NH3]=1.8×105

Step 3: Find [NH4+] and [OH] at equilibrium

To determine the equilibrium concentrations, we use an ICE table:
NH3(aq)NH4+OH
Initial1.50M00
Changex+x+x
Equilibrium1.50Mxxx
Plugging the equilibrium values into our Kb expression, we get the following:
Kb=(x)(x)1.50Mx=1.8×105
Simplifying, we get:
x21.50Mx=1.8×105
This is a quadratic equation that can be solved by using the quadratic formula or an approximation method. Either method will yield the solution
x=[OH]=5.2×103 M

Step 4: Find pH from [OH]

Now that we know the concentration of hydroxide, we can calculate pOH:
pOH=log[OH]=log(5.2×103)=2.28
Recall that at 25C, pH+pOH=14. Rearranging this equation, we have:
pH=14pOH
Plugging in our value for pOH, we get:
pH=14.00(2.28)=11.72
Therefore, the pH of the solution is 11.72.

Common weak bases

At left, structure of pyridine. On right, structure of a generic amine: a neutral nitrogen atom with single bonds to R1, R2, and R3.
Pyridine (left) is cyclic nitrogen-containing compound. Amines (right) are organic compounds containing a neutral nitrogen atom with three single bonds to hydrogen or carbon. Both molecules act as weak bases.
From soaps to household cleaners, weak bases are all around us. Amines, a neutral nitrogen with three bonds to other atoms (usually a carbon or hydrogen), are common functional groups in organic weak bases.
Amines act as bases because nitrogen's lone pair of electrons can accept an H+. Ammonia, NH3 is an example of an amine base. Pyridine, C5H5N, is another example of a nitrogen-containing base.

Summary

  • For a generic monoprotic weak acid HA with conjugate base A, the equilibrium constant has the form:
Ka=[H3O+][A][HA]
  • The acid dissociation constant Ka quantifies the extent of dissociation of a weak acid. The larger the value of Ka, the stronger the acid, and vice versa.
  • For a generic weak base B with conjugate acid BH+, the equilibrium constant has the form:
Kb=[BH+][OH][B]
  • The base dissociation constant (or base ionization constant) Kb quantifies the extent of ionization of a weak base. The larger the value of Kb, the stronger the base, and vice versa.

Try it!

Problem 1: Finding Kb from pH

A 1.50 M solution of pyridine, C5H5N, has a pH of 9.70 at 25C. What is the Kb of pyridine?
Choose 1 answer:

Want to join the conversation?

  • blobby green style avatar for user p4q4storm
    for the example 1: calculating the % dissociation, the part where the ICE table is used and you can use the quadratic formula to find concentration "x", the two answers I got for x was x= -0.01285M and x=0.01245M. You guys said the concentration I should have found is 0.0126M. I was trying to figure out which of the "x" is the correct one ( I assume since a negative concentration can not exist, the concentration has to be 0.01245M) and I have gone through my calculations a few times, and I don't know where I went wrong. Is it a rounding error?
    (8 votes)
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    • piceratops seed style avatar for user RogerP
      What you've calculated using the quadratic formula is correct. As you rightly say, you can't have a negative concentration, so the viable answer is 0.01245 M.

      If you use the small x assumption, then it comes out as 0.012649 M. You would expect a small difference in the result depending on which method is used. So it's strange that the article says that either method will give x=0.0126 M.

      My guess is that the author of the article probably used the small x method and perhaps didn't check the quadratic formula result.

      However, the difference is so small that it's negligible,
      (18 votes)
  • hopper jumping style avatar for user Yuya Fujikawa
    In example 1, why is the formula for % dissociation [A-]/[HA]*100% and not [H3O+]/[HA]*100% or [H3O+][A-]/[HA]*100%? Is this a stupid question? Sorry, if it is.
    (5 votes)
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  • duskpin seedling style avatar for user Hannah McGowen
    Is it possible to find the percent dissociation of a weak base, or is it only applicable to weak acids?
    (4 votes)
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  • hopper jumping style avatar for user Yuya Fujikawa
    So all of these are happening in water. What if these reactions aren't happening in water? Is there a situation like that? Like in gas? or something? Not something necessary to think about?
    (5 votes)
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  • female robot ada style avatar for user Romaa
    why are we making ICE tables here?
    (3 votes)
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  • aqualine ultimate style avatar for user Jadyn Newberry
    Well i'm a 3rd grader and I want to learn this and isn't OH weak?
    (2 votes)
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  • leaf green style avatar for user Bibika
    After reading the article I understood that ICE Table applies only to the weak acid and bases and not to the strong acid and bases. In case of the strong acid and base we can directly use the concentration of the compound given because it dissociates totally. I am correct right?
    (3 votes)
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    • aqualine ultimate style avatar for user Dulyana Apoorva
      I guess you are correct, because, as strong acids and bases dissociate completely in an aqueous solution, it is safe to say that their concentrations can be used in calculations. ICE literally stands for Initial, Change and Equilibrium, so, while it IS true that we have an equilibrium in even strong acids and bases, I think the reaction is favored so strong in the direction of the forward reaction of dissociation, so, the effect of the reverse reaction is negligible. Hence, there is no need for ICE tables.
      (1 vote)
  • blobby green style avatar for user mkiwan
    In the percent dissocation example above, and in the last step (step 4), why did we use the [HNO3] as 0.400 M rather than (0.400-x) which should be the more accurate concentration (after we found x=0.0126)?
    (2 votes)
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  • starky tree style avatar for user hammondkristen3
    Which is more dangerous: a dilute strong acid or a concentrated weak base.
    (2 votes)
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  • male robot hal style avatar for user Jayom Raval
    In the ICE tables, is the change always -x? If not, under what conditions would be higher (e.g. -2x or some other number)?
    Thank you
    (2 votes)
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