Acids and Bases Brnsted-Lowry acids and bases: During Aid-base reactions, H+ ions are exchanged.

Acids: Proton (H+) donors. Bases: Proton (H+) acceptors. An acid can only be a proton donor if there is a proton acceptor. Conjugate acid-base pairs: acids react to form bases and vise versa. The reactants and products only differ by one proton. Amphoteric substances: can act as either acids or bases. Amphoteric substances can: Dissociate to release H+ Can accept H+, hence they must have a lone pair of electrons. Lewis acids and bases: A base has a lone pair of electrons that are donated to the hydrogen ion. Acids: electron pair acceptors. Bases: electron pair donors. All Brnsted-Lowry acids are Lewis acids, but not all Lewis acids are Brnsted-Lowry acids. Soluble bases are known as alkali. They release the hydroxide ion (OH-) when dissolved.

Properties of acids and bases Acid-base indicators change colour reversibly according to the concentration of H+ ions in the solution. Indicator Litmus Methyl orange Phenolphthalein Reactions of Acids: Strong and weak acids and bases Strong acid/base: the equilibrium lies to the right the acid has dissociated fully. Strong acids exist virtually entirely as ions in solution. Weak acid/base: the equilibrium lies to the left the acid has only dissociated partially. Strong acids and bases will have a high concentration of ions in solution. This means that they will have a higher electrical conductivity and rate of reaction. Colour in Acid Pink Red Colourless Colour in alkali Blue Yellow Pink

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The pH scale The pH scale is a quantitative scale of acid strength based on the concentration of hydrogen ions.

Most pH values are positive, within the range of 1-14. The higher the concentration of hydrogen ions, the lower the pH. A change of one pH represents a 10-fold change in the concentration of hydrogen ions. The concentration of hydroxide ions is inversely proportional to the concentration of hydrogen ions. The higher the pH, the higher the concentration of OH-. Acid-base calculations Most acid-base reactions are in aqueous solutions. Water ionizes slightly at normal temperatures and pressures.

Since only a little water ionizes, the concentration of water remains virtually the same. Kw= Ionic product constant of water At 25C,

Equilibrium constants are temperature dependent. Increasing the temperature will shift the equilibrium to the right, increasing the concentrations of hydrogen and hydroxide ions, hence increases, and pH decreases. The concentrations of hydrogen and hydroxide ions can be found using the ionic product constant of water. The pOH scale is used to measure the concentration of hydroxide ions in a solution.

For all aqueous solutions:

This can be used if the pH is known, but pOH is not.

The pH and pOH of strong acids can be deduced from their concentrations.

We assume full dissociation, so we can calculate the ion concentration directly from the initial concentration of the solution. The concentration will follow the ratio of the coefficients in the balanced equation. This cannot be done for weak acids and bases, because they do not dissociate fully. To quantify the extent of dissociation, we use equilibrium considerations. The dissociation of acids and bases can be represented as equilibrium expressions with specific equilibrium constants. The value of the constant indicates the position of the equilibrium and the extent of dissociation. In aqueous reactions, he concentration of water is considered to be constant, as it does not change much. This leads to a modified equilibrium constant known as Ka (Acid dissociation constant)

The higher the acid dissociation constant, the greater the dissociation, and the stronger the acid. Kb (Base dissociation constant)

The higher the base dissociation constant, the greater the dissociation, and the stronger the base.

The equilibrium concentrations can be found through the change in concentration of the reactants and products. The change in concentration can be calculated using If the initial concentration is known, but the pH isnt, then algebra can be used. The change in concentration will be equal to x. Once the value of x is established, normal calculations are done. pKa and pKb Since the values of Ka and Kb are small, a logarithmic scale can be used.

The same applies for Kb. These values must be quoted at a specific temperature. The values of pKa and pKb are usually positive, and have no units. The relationship between pKa and pKb is inverse. The larger the pKa, the weaker the acid. The larger the pKb, the weaker the base. A unit change in of pKa or pKb represents a 10-fold change in of Ka or Kb. For a conjugate acid-base pair:

The higher the Ka of the conjugate acid, the lower the Kb of the conjugate base. (The stronger the acid, the weaker the base)

Buffer Solutions Buffer solutions are resistant to changes in pH on the addition of small amounts of acids and alkali. Acidic buffers: maintain the pH at a value less than 7. Acidic buffers are made by mixing an aqueous solution of a weak acid with a solution of its salt of a strong alkali. The salt fully dissociates in solution, hence there will be a high concentration of the weak acid and its conjugate base. These two substances are ready to react with added hydrogen or hydroxide ions to neutralise them, hence the pH remains largely unchanged. Basic Buffers: Maintain the pH at a value greater than 7. Acidic buffers are made by mixing an aqueous solution of a weak base with a solution of its salt of a strong acid. The salt fully dissociates in solution, hence there will be a high concentration of the weak base and its conjugate acid. The buffers acid neutralises added alkali. The buffers base neutralises added acids.

The dissociation of the weak acid is small, hence its concentration remains mostly unchanged. The salt is fully dissociated, hence the concentration of the ions will be the same as the initial concentration of the salt.

The acids in buffer solutions are usually have pKa values as close to the required pH of the buffer as possible. The same applies for basic buffers, with pKb values and pOH. The acid or base are then reacted with a strong alkali or base respectively, until one half is converted into salt. The final mixture is a buffer containing equal amounts of the salt as the acid/base. Dilution does not change the ratio of acid to base to salt, hence the pH remains the same regardless of volume. However, the buffering capacity will be reduced. Temperature affects the values of Ka and Kb, hence the pH of the buffer. This means that temperature must be kept constant.

Salt Hydrolysis Neutralization reactions between acids and bases produce a salt. Salt: ionic compound containing a cation from the parent base, and an anion from the parent acid. Not all salt are neutral their pH depends on their ability to react with water hydrolyse, releasing H+ or OH- ions. The ions are the conjugate acids and bases of the parent acids and bases, hence the stronger the parent molecule, the weaker the product. Anion hydrolysis: The anion (A-) is a conjugate base of the parent acid. If the acid is weak, the base will be strong enough to hydrolyse water.

As hydroxide ions are released, the pH is increased. Cation hydrolysis: The cation (M+) is the conjugate of the parent base. When the base is weak, and the conjugate is non-metal, it is able to hydrolyse water. Metal ions that are small with a high charge density (two or three positive charges) can hydrolyse water. Ions that are able to hydrolyse water: Be2+, Al3+, Fe3+ Cations from group 1 and 2 do not have sufficient charge density to hydrolyse water to generate H+, hence they do not show acidic behavior. The pH of a salt solution depends on the relative hydrolysis of its anions and cations. This can be deduced from the relative strengths of the parent acids and bases. Salts of strong acids and bases are neutral.

Acid-base titration Titration: the controlled neutralisation reaction between acids and bases. The reactants are missed together until an equivalence point is reached, where the two reactants neutralise each other completely. This point is reached when stoichiometrically equivalent amounts of acid and base have been reacted together. The solution will only contain salt and water. The change in pH is not a linear relationship with the volume of base added to an acid. Point of inflection: a big rise in pH at the equivalence. Half-equivalence point: a point when half of a weak acid has reacted with a strong base, creating a salt. This makes it a buffer; hence pH rises will be slow. Indicators Indicators change colour according to the pH of the solution. They are weak acids or bases in which the dissociated and undissociated forms have different colours. The colour changes visually as the equilibrium shifts between reactants and products, depending on the pH of the medium. Change point: the pH at which an indicator changes colour. When the concentrations of the acidic indicator and its conjugate base are equal, the indicator is in the middle of its colour change. The indicator used must have an end points coinciding with its pH at equivalence point.