PowerPoint to accompany

Chapter 14
Acid-Base Equilibria
Dr V. Paideya
2012

Some Definitions

Arrhenius

Acid: Substance that, when dissolved in water, increases the concentration of hydrogen ions.
Base: Substance that, when dissolved in water, increases the concentration of hydroxide ions.

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Some Definitions

BrnstedLowry

Acid: Proton donor

Base: Proton acceptor

If it can be either an acid or base, it is amphiprotic. E.g. HCO3 , HSO4 , H2O

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What Happens When an Acid Dissolves in Water?

Water acts as a BrnstedLowry base and abstracts a proton (H+) from the acid.
As a result, the conjugate base of the acid and a hydronium ion are formed.

Figure 14.2

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Conjugate Acids and Bases

From the Latin word conjugare, meaning to join together.

Reactions between acids and bases always yield their conjugate bases and acids.

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Amphiprotic solvents
Solvents that can exhibit both acidic and basic character are called amphiprotic solvents. Eg. The hydrogen sulfite ion (HSO3- ) Write an equation for the rxn of HSO3- with water, in which the HSO3- ion acts as: (a) An acid (b) A base In both cases identify the conjugate acid-base pairs
Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Soln:
(a)

(b)

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Weak Bases
Bases react with water to produce hydroxide ion (OH-)

NH3(aq) + H2O(l) NH4+(aq) + OH- (aq)

Base Acid Conjugate acid Conjugate base

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Acid and Base Strength

Strong acids are completely dissociated in water.

Their conjugate bases are quite weak.

Weak acids only dissociate partially in water.

Figure 14.3

Their conjugate bases are weak bases.

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Acid and Base Strength

Substances with negligible acidity do not dissociate in water.

Their conjugate bases are exceedingly strong.

Figure 14.3
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Acid and Base Strength

In any acid-base reaction, the equilibrium will favour the reaction that moves the proton to the stronger base.
HCl(aq) + H2O(l) H3O+(aq) + Cl(aq)

H2O is a much stronger base than Cl, so the equilibrium lies so far to the right, K is not measured (K>>1).

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Acid and Base Strength

C2H3O2(aq) + H2O(l)
Base Acid

H3O+(aq) + C2H3O2(aq)
Conjugate base conjugate acid

Acetate is a stronger base than H3O+, so the equilibrium favours the left side (K < 1).

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Autoionisation of Water

As we have seen, water is amphoteric.

In pure water, a few molecules act as bases and a few act as acids.
H3O+(aq) + OH(aq)

H2O(l) + H2O(l)

This is referred to as autoionisation.

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Ion-Product Constant

The equilibrium expression for this process is: Kc = [H3O+] [OH] = [H+] [OH] This special equilibrium constant is referred to as the ion-product constant for water, Kw. At 25C, Kw = 1.0 1014
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pH

pH is defined as the negative logarithm (in base 10) of the [H+] ion concentration. pH = log [H+]
Also sometimes seen as pH = -log [H3O+]

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Exercise

In a sample of lemon juice [H+] is 3.8 x 10-4 M. What is the pH of the lemon juice?

pH = -log [H+] = - log (3.8 x 10-4 M) = 3.4 (remember rules for significant figures)

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

EXERCISE Cont.

Calculating [H+] from pH

A sample of freshly squeezed apple juice has a pH of 3.76. Calculate [H+].

pH = - log [H+] = 3.76 log [H+] = -3.76

[H+] = antilog (-3.76) = 10-3.76 = 1.7 x 10-4 M
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Other p Scales

The p in pH tells us to take the negative log of the quantity (in this case, hydrogen ions) Some similar examples are
pOH
pKW

= - log [OH-] = -log KW

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

pH

In pure water,

Kw = [H+] [OH] = 1.0 1014

Because in pure water [H+] = [OH],

[H+] = (1.0 1014)1/2 = 1.0 107

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

pH

Therefore, in pure water, pH = log (1.0 107) = 7.00 An acid has a higher [H+] than pure water, so its pH is <7.

A base has a lower [H+] than pure water, so its pH is >7.

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pH

These are the pH values for several common substances.

Figure 14.4
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pH
Because, [H+] [OH] = Kw = 1.0 1014, we know that log [H3O+] + log [OH] = log Kw = 14.00

or, in other words, pH + pOH = pKw = 14.00

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

How Do We Measure pH?

For less accurate measurements, one can use:

Litmus paper Red paper turns blue above ~pH = 8 Blue paper turns red below ~pH = 5

An indicator (see table below) For more accurate measurements, one uses a pH meter, which measures the voltage in the solution.

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Strong Acids

You will recall that the seven strong acids are HCl, HBr, HI, HNO3, H2SO4, HClO3 and HClO4.

These are, by definition, strong electrolytes and exist totally as ions in aqueous solution. For the monoprotic strong acids: [H+] = [acid].
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Calculating the pH of a Strong Acid

What is the pH of a 0.040 M solution of HClO4?

Since HClO4 is a strong acid, it is completely ionized giving [H+] = [ClO4-]

The pH of the solution is given by

pH = -log(0.040) = 1.40

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Strong Bases

Strong bases are the soluble hydroxides, which are the alkali metal and heavier alkaline earth metal hydroxides (Ca2+, Sr2+ and Ba2+).

Again, these substances dissociate completely in aqueous solution.

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Calculating the pH of a Strong Base

What is the pH of a 0.0011 M solution of Ca(OH)2? Ca(OH)2 is a strong base that dissociates in water to give two OH- ions per formula unit. Thus, the concentration of OH- (aq) for the solution is 2 x (0.0011 M) = 0.0022 M

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Solution:

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Dissociation Constants

For a generalised acid dissociation:

A(aq) + H3O+(aq) A(aq) + H+(aq) or HA(aq)

HA(aq) + H2O(l)

the equilibrium expression would be

K =

[H+] [A] [HA]

This equilibrium constant is called the aciddissociation constant, Ka.

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Dissociation Constants
The greater the value of Ka, the stronger the acid.

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating Ka from the pH

The pH of a 0.10 M solution of formic acid, HCOOH, at 25C is 2.38. Calculate Ka for formic acid at this temperature.
HCOOH(aq) H+(aq) + HCOO(aq)

From the equation:

[H+] [COO] Ka = [HCOOH]
Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating Ka from the pH

The pH of a 0.10 M solution of formic acid, HCOOH, at 25C is 2.38. Calculate Ka for formic acid at this temperature.

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating Ka from the pH

To calculate Ka, we need the equilibrium concentrations of all three things. We can find [H+], which is the same as [HCOO], from the pH. pH = log [H+] 2.38 = log [H+]
2.38 = log [H+] 102.38 = 10log [H+] = [H+] i.e. 4.2 103 = [H+] = [HCOO]
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raising to the power of 10 gives

Calculating Ka from pH

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating Percent Ionisation

Percent Ionisation =

[H+]eq [HA]initial

100

In this example: [H+]eq = 4.2 103 M [HCOOH]initial = 0.10 M

4.2 103 Percent Ionisation = 0.10 = 4.2%

100

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Calculating pH from Ka

Calculate the pH of a 0.30 M solution of acetic acid, HC2H3O2, at 25C. HC2H3O2(aq) H+(aq) + C2H3O2(aq)

Ka for acetic acid at 25C is 1.8 105.

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Calculating pH from Ka

The equilibrium constant expression is

[H+] [C2H3O2] Ka = [HC2H3O2]

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating pH from Ka

We are assuming that x will be very small compared to 0.30 and can therefore be ignored

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating pH from Ka
2 ( x ) Now: 1.8 105 = (0.30)

(1.8 105) (0.30) = x2

5.4 106 = x2
2.3 103 = x

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Calculating pH from Ka
Since pH = log [H+]
then pH = log (2.3 103)

pH = 2.64
Finally, check the assumption that 0.30 - x 0.30. In fact, 0.30 - 0.0023 0.30 and the assumption is valid.

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How to check if this approximation is valid

If (2.3 x 10-3 /0.30) x 100% is less than 5%, then the approximation is valid In the above example, 0.77% < 5% therefore the assumption is valid If x > 5% then use the quadratic equation to solve for x

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Weak Bases

Bases react with water to produce hydroxide ion.

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Weak Bases

The equilibrium constant expression for this reaction is:

[NH4+] [OH] Kb = [NH3]

where Kb is the base-dissociation constant.

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

Weak Bases

Kb can be used to find [OH] and, through it, pH.

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

pH of Basic Solutions

What is the pH of a 0.15 M solution of NH3?

NH4+(aq) + OH(aq)

NH3(aq) + H2O(l)

[NH4+] [OH] 5 Kb = = 1.8 10 [NH3]

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

pH of Basic Solutions

Brown, LeMay, Bursten, Murphy, Langford, Sagatys: Chemistry 2e 2010 Pearson Australia

pH of Basic Solutions

2 ( x ) 1.8 105 = (0.15)

(1.8 105) (0.15) = x2 2.7 106 = x2 1.6 103 = x2

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pH of Basic Solutions
Therefore, [OH] = 1.6 103 M pOH = log (1.6 103) pOH = 2.80
Since pH + pOH = 14

then

pH = 14.00 2.80
i.e. pH = 11.20

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Ka and Kb

Ka and Kb are related Ka Kb = Kw Taking logs gives pKa + pKb = pKw i.e. pKa + pKb = 14
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Effect of a Cation and an Anion in Solution

1. An anion that is the conjugate base of a strong acid, for example Br-, will not affect the pH of the solution.
2. An anion that is the conjugate base of a weak acid, for example CN-, will cause an increase in pH. 3. The cations of group 1 and heavier members of group 2 (Ca2+, Sr2+ and Ba2+) will not affect pH.

4. Other metal ions will cause a decrease in pH. 5. When a solution contains both the conjugate base of a weak acid and the conjugate acid of a weak base, the ion with the larger equilibrium constant Ka or Kb, will have the greater influence on the pH of the solution.
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Factors that Affect Acid Strength

Oxyacids

These are acids in which the OH group and possible additional oxygen atoms are bound to a central atom, Y, e.g. H2SO4 {O2S(OH)2}, ClOH, HNO3 {O2NOH}. For oxyacids with a different central atom (but having the same number of OH groups and O atoms) acidity increases with increasing electronegativity.

i.

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Factors that Affect Acid Strength

Oxyacids
ii.

For a series of oxyacids with the same central atom, Y, acidity increases with the number of oxygens.

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