TOPIC 9 Acids and Bases 9.

1 Properties of acids and bases ACID BASE

5. With carbonate to give salt, water and carbon dioxide 2HCl + CaCO3 CO2 + H2O + CaCl2. 6. With hydrogen carbonates to produce salt, water and carbon dioxide. HCl + NaHCO3 NaCl + H2O + CO2 Experimental properties of acids and bases when acids and bases neutralize, the reaction is noticeably exothermic (ie heat can be felt coming from the reaction). ARRHENIUS THEORY 1. ACID A substance when dissolves in water, it dissociates to form H+ ions. HCl H+ + ClHCl + H2O H3O+ + Cl-

Substance that produces H+ ions in aqueous solution. pH < 7 Turn blue litmus red

Substance that can neutralize an acid. An alkali is a base that is soluble in water. pH > 7 Turn red litmus to blue.

Indicators change color depending on whether they're in acidic or basic conditions Methyl orange Acid Bas e red yellow Bromophenol blue yellow blue Methyl red red yellow Bromothymol blue yellow blue Phenolphtalei n colorless red

2. BASE A substance when dissolves in water it produces OH- ions NaOH + Na+ + OH-

Reaction of acids with bases: 1. With hydroxide forming salt and water HCl + NaOH NaCl + H2O 2. With metal hydroxide forming salt and water 2HCl + Na2O 2NaCl + H2O 3. With ammonia forming salts HNO3 + NH4 NH4NO3 4. With reactive metals to yield salt and hydrogen gas 2HCl + Mg MgCl2 + H2

BRONSTED-LOWRY ACIDS AND BASES 1. ACID A substance that gives proton (hydrogen ions, H+ ) A proton donor 2. BASE A substance that receives a proton from another substance A proton acceptor

HOW TO IDENTIFY BRONSTED-LOWRY ACIDS AND BASES? 1. ACID A substance must contain a hydrogen atom attached by a bond that easily broken Example: HCl, HNO3 cations, anions that contain transferable protons NH4+, H2SO4-, HCO32. BASE A substance must have a non-bonding pair of electron pair that can be used to form a bond to a hydrogen ion. (usually this lone pair of electrons is on an oxygen or nitrogen atom) NH3, NaOH, H2O, F-, OHnormal Brnsted-Lowery equation:

CONJUGATE ACID-BASE PAIRS Chemical species whose formula differ only by one proton. CONJUGATE ACID A species formed when a base accepts a proton CONJUGATE BASE A species formed when a base donates a proton. The conjugate base will always have one less H atom that the acid (or the acid one more than the base) 9.3 Strong and weak acids and bases MONOPROTIC ACID Acid that can donate one proton only HCl, HNO3 DIPROTIC ACID Acid that can donate two protons H2SO4 AMPHIPROTIC Substance that can act as an acid and as a base.

acid + base

acid + base (proton transfer reaction) NO2-(aq)+ H3O+(aq)

example: HNO2(aq) + H2O(aq)

Each acid has a conjugate base and each base has a conjugate acid. These conjugate pairs only differ by a proton. In this example: NO2- is the conjugate base of the acid HNO2 H3O+ is the conjugate acid of the base H2O

a) H2PO4 Acid: H2PO4 HPO42 + H+ Base: H2PO4 + H+ H3PO4 b) H2O Acid: H2O OH + H+ Base: H2O + H+ H3O+ c) HSAcid: Base: HS H+ + S2 HS + H+ H2S

LEWIS THEORY LEWIS ACID 1. A species that accept a pair of electrons to form dative bonds 2. Electron pair acceptor 3. Example: H+ , cations ( Cu2+, Al3+) 4. Neutral molecules that have vacant valence orbitals that can accept a pair of electrons donated by a Lewis base. LEWIS BASE 1. A species that donate a pair of electrons 2. Anions 3. Molecules that have non-bonding pair of electron 4. All Lewis Bases are Bronsted-Lowry bases. LEWIS ACID-BASE REACTION 1. Involve the formation of a new covalent bonds in which both electrons are provided by one species. 2. Such bonds is called dative covalent bond. 3. Example:

WEAK ACID Acid that slightly dissociate(ionized) in dilute aqueous solution produces low concentration of H+ ions.

STRONG BASES 1. Group one hydroxide ( for example: NaOH, KOH) 2. Barium Hydroxide ( Ba (OH)2) WEAK BASE 1. Example: NH3 aquaeous ethylamine NH3 + H2O NH4+ + OH2. For a given some concentration of acid/base solution HCl (1M) CH3COOH (1M) NaOH (1M) NH3 pH 0 pH 5 pH 14 pH 9

THE pH SCALE pH is the negative of the logarithm of the hydronium ion concentration in a solution. pH = - log [ H3O+] OR pH = - log [H+] [H+] increases, pH decreases [H+] decreases, pH increases STRONG ACIDS AND BASES STRONG ACID Acid that dissolves in water completely ionized giving high concentration of H+ ions. HX H+ + X Example: HCl, HNO3, H2SO4 If the concentration of the H3O+ ion in pure water at 25oC is 1.0 x 10-7 M, the pH of pure water is 7. pH = -log [H3O+] = -log (1.0 x 10-7) = 7 When the pH of a solution is less than 7, the solution is acidic. When the pH is more than 7, the solution is basic. Acidic: Basic: pH < 7 pH > 7

For example: HCl H+ + ClHCl H+ Cl0.001 M 0.001 M 0.001 M pH = - log [H ] = - log [0.001] =3 HCl 0.01 M 0.1 M 1.0 M Dissociation constant, Kc H2O OH + H+ H2O + H2O H3O + OH[ [ [ [ ][ ] ][ ] ] ] pH 2 1 0
+

= (1.0 x 10-7 M) (1.0 x 10-7 M) = 1.0 x 10-14 M Kw varies with temperatures. Temperature increase, Kw increase. Equilibrium shift to the right. Concentration of [H+] increase, the acidity increase. Example: If an acid has an H+ concentration of 0.0001 M, find the pH. First convert the number to exponential notation, find the log, then solve the pH equation. H+ = 0.0001M = 10-4; log of 10-4 = -4; pH = - log [ H+] = - log (10-4) = - (-4) = +4 = pH The purpose of the negative sign in the log definition is to give a positive pH value. Example: If the base has an OH- concentration of 0.001M, find the pH. Solution: To find the pOH, (similar to finding the pH,) then subtract the pOH from 14. OH- = 0.001M = 10-3; pOH = -log [OH-] = -log (10-3) = +3 = pOH pH = 14 - pOH; pH = 14 - 3 = 11 = pH WEAK ACID AND BASE (PARTIALLY IONISED) FOR THE REACTIONS OF DISSOCIATION OF ACID:

Calculation:

Kc [H2O] = [H+][ OH ] Since ionization is very low, [H2O] is constant Kc [H2O] = another constant = Kw = [H+][ OH ] at 25oC, [H3O+ ] = [H+] =1.0 x 10-7 M so, Kw = [H+][ OH ]

stepwise dissociation constants are defined as

pH

7.0 FOR THE REACTIONS OF DISSOCIATION OF BASE:

25 stepwise dissociation constants are defined as

Temperature (oC)

18.1.3 Solve the problems involving [H+(aq)], [OH-(aq)], pH and pOH. CALCULATIONS INVOLVING ACID/BASE 18.1.1 State the expression for the ionic product constant of water (Kw). Pure water at 25C : [H+] and [OH-] are equal = 1.00 x 10-7 mol2 dm-6. This is known as dissociation constant of water, Kw. [ ][ ] pH = -log [H+] pOH = 14 - pH ; [H+] = 10-pH

18.1.4 State the equation for the reaction of any weak acid or weak base with water, and hence deduce the expressions for Ka and Kb. The greater the (acid/base) dissociation constant, the stronger the acid. In water, the acid/base will dissociate: Reactants (aq) products(aq) [ ] [ ] Eg: weak acid: HA(aq) H+(aq) + A- (aq) [ ][ ] [ ]

18.1.2 Deduce [H+(aq)] and [OH-(aq)] for water at different temperatures given Kw values. Dissociation of water molecule=breaking of bond, therefore the forward reaction is endothermic. When temperature raise, the equilibrium shifted to the endothermic side (right), hence the equilibrium constant increases. When equilibrium constant increases, [H+]>10-7mol dm-3, pH of pure water at higher volume <7.

Eg: weak base: Kb =

B(aq)+H2O(l) BH+(aq)+OH (aq)

[ ][ [ ] ]

18.1.5 Solve problems involving solutions of weak acids and bases using the expressions: Ka x Kb = Kw pKa + pKb = pKw pH + pOH = pKw [H+] concentration [OH-] concentration WEAK ACID Ka =
[ [ ][ ] ]
+

*where a = concentration of acid at equilibrium 18.1.6 Identify the relative strengths of acids and bases using values of -log [H+] pH -log [OH-] pOH pKa= -log Ka
[ ] pH=pKa+log [ ]

Ka, Kb, pKa and pKb.

The larger the Ka/Kb value, the stronger the acid/base. The larger the pKa/pKb value, the weaker the acid/base.

equilibrium
[ [ ] ]

constant [H ]= Given: HA(aq) Initial concentrations Concentrations at equilibrium Changes in concentrations A ax -x A-(aq) 0 x +x 0 x +x H+(aq) +

BUFFER SOLUTIONS 18.2.1 Describe the composition of a buffer solution and explain its action. Buffer solution is a solution of weak acid and its salt or a solution of a weak base and its salt. Effective buffer: the concentration of the buffer solution must be greater than the concentration of the strong acid/base added. Ways to prepare buffer solution: 1. Mix solution of weak acid/base and a salt of the weak acid/base. (eg. Ethanoic acid and sodium ethanoate.) 2. Add a little strong acid to excess weak base/add a little strong base to excess weak acid. (eg. A little sodium hydroxide and excess ethanoic acid.)

When the pKa value is very small, assume that the x

[ [ ][ ] ]

*the concentrations in the equation must be concentrations at equilibrium. Therefore, let

Adding strong acid Solution of ethanoic acid and sodim ethanoate Eq: CH3COOH CH3COO- + H+ -The H from the strong acid added will react with the conjugate base CH3COO-. CH3COO- + H+ CH3COOH -The H+ will be removed from the solution & therefore its concentration returns back to almost its original concentration. -Hence the pH of the solution rises again. Solution of ammonia and ammonium chloride Eq: NH3 + H2O NH4+ + OH-The H+ from the strong acid will react with the undissociated NH3. NH3 + H+ NH4+ -The H+ will be removed from the solution and therefore its concentration returns back to almost its original concentration. -Hence the pH of the solution rises back.
+

Adding strong base -The OH from the strong base added will react with the undissociated CH3COOH. CH3COOH + OH- CH3COO+ H2O -The OH- will be removed from the solution and therefore its concentration return back to almost its original concentration. -Hence the pH of the solution decrease back. -The OH- from the strong base added will react with the conjugate acid NH4+. NH4+ + OH- NH3 + H2O -The OH- will be removed from the solution and therefore its concentration return back to almost its original concentration. -Hence the pH of the solution rises back.
-

Buffer is most effective when concentration of acid and base are equal, and the pH is equal to the pKa value.

Eg: Solid sodium ethanoate is added to 0.200 mol dm-3 ethanoic acid untl its concentration is 0.0500 mol dm-3. Given that Ka for ethanoic acid is 1.74 x 10-5 mol dm-3, and assuming no volume change on dissolving the solid, calculate the pH of the buffer solution formed. Sol:

18.2.2 Solve problems involving the composition and pH of a specified buffer system. The pH of the buffer solution depends on the Ka of the weak acid/base inside the buffer solution ad also the ratio of the concentration of the acid/base and its conjugate base/acid. The pH of the buffer will not change when diluted, but it will be less effective.

SALT HYDROLYSIS 18.3.1 Deduce whether salts form acidic, alkaline or neutral aqueous solutions. Derived from: Strong acid Strong base

Titration curve of strong acid and strong base.

Strong acid

Weak base

Weak acid

Strong base

Weak acid

Weak base

Contain highly charged ions (complex ion)

pH and explanation pH = 7 When the cation/anion derived from strong base/acid, the weaker the acid-base activity of the ions (weak conjugate acid/base). pH < 7 Eg: NH3 + H2O NH4+ + OHCation produced from the dissociation of the weak base will act as a strong conjugate acid and react with water to form more H+ ions. Eg: NH4+ NH3 + H+ Therefore, the pH will be lower than 7. pH > 7 Eg: CH3COOH CH3COO- + H+ Features (when strong base added little by little into the strong acid): The anion produced from the dissociation of the weak acid will act as a strong conjugate base and react with water to form more ions.small increase in pH around pH 1 when H+ ions are still in a)OH Steady Eg: CH3COO + H2O CH3COOH + OH excess. Therefore, the pH will be higher than 7. b) Sudden pH depends on the value of pKa and pKb of the ions inside the salt rapid change in pH at equivalence point. c) Steady small increase in pH around 13 when OH- ions are in excess. solution. d) Almost any common acid-base indicator will work for this type of Approximately neutral. Eg: [Al(H2O)6]3+ , [Fe(H2O)6]3+ titration. Electron attracting power of the ions weakens the O-H bonds in H2O. H-O-H H-O--------H Titration curve of weak acid and strong base. Stabilized by complex ion 3+ [Al(H2O)6] [Al(OH)(H2O)5]2+ + H+ The solution becomes quite acidic.

ACID-BASE TITRATIONS 18.4.1 Sketch the general shapes of graphs of pH against volume for titrations involving strong and weak acids and bases and explain their important features.

 Features (when strong base is added little by little into the weak acid): a) Steady increase in pH, 2<pH<7, when H+ ions are still in excess. b) Sudden rapid change in pH at equivalence point. c) pH at equivalence point >7 d) Steady small increase in pH around 13 when OH- ions are in excess. e) Suitable indictor: Phenolphthalein. Titration curve of strong acid and weak base.

Titration curve of weak acid and weak base.

Features (when weak base added little by little into the weak acid): a) Steady increase in pH, 2<pH<7, when H+ ions are still in excess. b) Acceptable change in pH at equivalence point. c) Steady increase in 7<pH<12 when OH- ions are in excess. d) Hard to find suitable indicator. INDICATORS 18.5.1 Describe qualitatively the action of an acid-base indicator. Indicator is a substance (often an organic dye) that has different colour in acidic and alkaline solutions and hence can be used to detect the end point of a titration. Indicators are weak acid/base in the two forms have different colours and are in equilibrium with each other: HIn H+ + InRed Blue

Features (when weak base is added little by little into the strong acid): a) Steady small increase in pH around pH 1 when H+ ions are still in excess. b) Sudden rapid change in pH at equivalence point. c) pH at equivalence point <7 d) Steady increase in pH, 7<pH<12, when OH- ions are in excess. e) Suitable indictor: Methyl orange.

Litmus:

In acidic solution A lot of H+ ions present Equilibrium shifted to the left Red colour seen

In alkaline solution OH- ions are reacted with H+ ions (reduced H+ ions) Equilibrium shifted to the right Blue colour seen

18.5.2 State and explain how the pH range of an acid-base indicator relates to its pKa value. When pH=pKa, the two coloured forms will have equal concentration and the indicator will be in the middle of its colour change. [HIn]=[In-], equilibrium balanced between the acid and its conjugate base. [ ][ ] Ka= [] Ka=[H+] pKa=pH

18.5.3 Identify an appropriate indicator for a titration, given the equivalence point of the titration and the pH range of the indicator.