Acid-Base Equilibriam

prepared by Dr.Kalaiarasu
 Acid-Base Definitions

• A Lewis Acid is a substance that accepts a pair of electrons

• A Lewis Base is a substance that donates a pair of electrons

• A Bronsted-Lowry Acid is a substance that donates a proton

• A Bronsted-Lowry Base is a substance that accepts a proton

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• Each acid is linked to a conjugate base on the other side of the equation
HCl(g) + H2O(l) –> H3O+(aq) + Cl-(aq)

• Strong Acids are acids that completely dissociate

e.g. HCl(aq) –> H+(aq) + Cl-(aq)

• Weak Acids are acids that don’t completely dissociate

e.g. CH3COOH(aq) –> CH3COO-(aq) + H+(aq)

• Monoprotic acids only donate one proton to an aqueous solution.

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 pH calculations
• The acidity of a solution is based off of the concentration of protons in an aq
ueous solution [H+]
pH = -log[H+]
e.g. For a 0.1M solution of HCl, the pH will be -log[0.1] = 1.00

• [H+] = 1×10^-pH
e.g. For a solution of pH 2.00 the concentration of protons present will be
1X10^-2.00 = 0.01M

• For a monoprotic strong acid, the concentration of H+ ions present will be th

e same as the concentration of the acid

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 Acid-Base Equilibria and Kw
• In all aqueous solutions and pure water, the following equilibrium occurs:
H2O(l) ⇌ H+(aq) + OH-(aq)

• Therefore the following equilibrium expression occurs:

Kc = [H+(aq)][OH-(aq)] => Kc x [H2O(l)] = [H+(aq)][OH-(aq)][H2O(l)]

• The Kw expression is equal to the Kc of the above equilibrium multiplied

by the concentration of water so Kw = [H+(aq)][OH-(aq)]

• At 25C the value of Kw for all aqueous solutions is 1×10^-14 mol2 dm-6

• The Kw expression can be used to calculate the value of [H+(aq)] if the

value of [OH-(aq)] is known
pKw = -log(Kw) so Kw = 10^-pKw
If Kw =1×10^-14 then pKw = 1
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Finding pHs of Pure Water and Strong Base
s
pH of Pure Water

• Pure water is neutral because the concentration of H+ ions is equal to the c

oncentration of OH- ions
• Using Kw = [H+][OH-] then we can say Kw = [H+]^2 so the square root of K
w = [H+]
• At 25C [H+(aq)] = √1×10^-14 = 1×10^-7 so pH = 7.00

pH of a Strong Base

• For strong bases, the concentration of OH- ions is usually given so the conc
entration of H+ ions is required in order to work out the pH
• For a solution of 0.1M NaOH:
[H+] = Kw/[OH-] = 1×10^-14 / 0.1 = 1×10^-13 mol dm-3
• pH = -log(1×10^-13) = 13.00

prepared by Dr.Kalaiarasu
 Finding pHs of Weak Acids and Ka
• Weak Acids only slightly dissociate when in water so form the equilibrium:
HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq) or
HA(aq) ⇌ H+(aq) + A-(aq)

• This equilibrium can give an expression for Ka:

Ka = [H+][A-]
[HA]

• The Ka value of an acid can be used to determine the concentration of H

+ ions and thus the pH.

• The half equivalence point is the position when the concentration of added b
ase is equal to half the original concentration of acid
Assuming that [HA] = [A-] then pH = pKa

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 Diluting an Acid or Alkali

• Dilutions of an acid or alkali can be worked out by the following equations:

[H+]new = [H+]old x (old volume / new volume)

[OH-]new = [OH-]old x (old volume / new volume)

• These new values can be used in the pH equation to work out the new pH o
f a solution

pH = -log[H+]

• pH is a logarithmic scale so diluting a strong acid 10 times will increase its p

H by one unit and 100 times will increase its pH by two units
• Weak acids will increase by less than one unit for being diluted 10 times
• Diluting a weak acid pushes the equilibrium to the right

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 Buffer Solutions
• A buffer solution is one where the pH does not change significantly if small a
mounts of acid or alkali are added to it

• An acidic buffer solution is made from a weak acid and a salt of that weak a
cid(made by reacting the weak acid with a strong base)
e.g. CH3COOH and CH3COO-Na+

• A basic buffer solution is made from a weak base anf a salt of that weak ba
se(made by reacting the weak base with a strong acid)
e.g. NH3 and NH4+Cl-

• An ethanoic acid buffer works by creating an equilibrium between the acid a

nd conjugate base:
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)

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• In a buffer solution there is a higher concentration of the salt CH3COO- ion t
han in the pure acid

• If small amounts of acid is added to the buffer, the above equilibrium will shif
t to the left removing nearly all the H+ ions

• As there is a large salt ion concentration, the ratio of [CH3COOH]:[CH3CO

O-] stays relatively constant so therefore the pH remains similar

• If small amounts of alkali is added to the buffer, OH- ions react with the H+ i
ons to form water and the equilibrium will shift to the right to produce more
H+ ions

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 Calculating pH of Buffers

• The Ka equation is used in order to determine the pH by finding the concent

ration of H+ ions present in the solution first
Ka = [H+][A-]
[HA]

pH = -log[H+]

• The equation is assuming that the [A-] concentration is due to the added salt
onlyand that the initial concentration of acid has remained constant

• The salt content can be added as a solution or a solid

• A buffer can also be made by partially neutralising a weak acid with alkalith
erefore making a salt

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 Titration Curves
• Titration curves show the change in pH when a volume of an acid or a base
is added

Constructing Titration Curves

• Measure the initial pH of the acid

• Add alkali in small amounts noting the volume added
• Stir the mixture to equalise the pH
• Measure and record the pH to 1 decimal place
• When approaching the end point add in smaller volumes of alkali
• Add alkali until in excess

-The equivalence point lies at the midpoint of the extrapolated vertical position
of the curve
-The meter must be calibrated first by measuring a known pH of buffer solution
as pH meters can lose accuracy on storage
-Accuracy can be improved by maintaining a constant temperature
prepared by Dr.Kalaiarasu
prepared by Dr.Kalaiarasu
 Indicators
• Indicators can be considerred as a weak acid. The acid must have a differen
t colour to its conjugate base
• An indicator changes colour from HIn to In- over a narrow range
HIn(aq) ⇌ H+(aq) + In-(aq)
• Le Chateliers Principle can be applied to give the colour change
• In an acid solution, the H+ ions present will push the equilibrium towards the
reactants and therefore the colour of HIn will be displayed
• In an alkaline solution, the OH- ions present will react and remove H+ ionsc
ausing a shift to the products and therefore the colour of In- will be displaye
d
• The end point in a titration is reached when [HIn] = [In-] so an indicator who
se end point coincides with the equivalence point should be chosen
• An indicator will work if the pH range of the indicator lies on the vertical part
of a titration curve

• Phenolphthalein – Strong Bases: Colourless (acid) –> Pink (alkali)

• Methyl Orange – Strong Acids: Red (acid) –> Yellow (alkali)

prepared by Dr.Kalaiarasu
Thank you

prepared by Dr.Kalaiarasu