ACID BASE CHEMISTRY

Acid and Bases .

Acid and Bases .

Acid and Bases .

Citrus fruits contain citric acid. Vinegar is a solution of acetic acid. . Feel slippery. React with carbonates and bicarbonates to produce carbon dioxide gas Bases Have a bitter taste. React with certain metals to produce hydrogen gas.Acids Have a sour taste. Many soaps contain bases.

Some Properties of Acids Produce H+ (as H3O+) ions in water (the hydronium ion is a hydrogen ion attached to a water molecule) Taste sour Corrode metals Electrolytes React with bases to form a salt and water pH is less than 7 Turns blue litmus paper to red ³Blue to Red A-CID´ .

Some Acids ‡ HI (aq) ‡ HCl (aq) ‡ H2SO3 ‡ HNO3 ‡ HIO4 .

chalky Are electrolytes Feel soapy. slippery React with acids to form salts and water pH greater than 7 Turns red litmus paper to blue ³Basic Blue´ .ions in water Taste bitter.Some Properties of Bases Produce OH.

Some Common Bases NaOH KOH Ba(OH)2 sodium hydroxide caustic soda potassium hydroxide liquid soap barium hydroxide stabilizer for plastics ³MOM´ Milk of Mg(OH)2 magnesium hydroxide magnesia Al(OH)3 aluminum hydroxide Maalox (antacid) .

ions (problem: some bases don¶t have hydroxide ions!) .Acid/Base definitions ‡ Definition #1: Arrhenius (traditional) Acids ± produce H+ ions (or hydronium ions H3O+) Bases ± produce OH.

in water .Arrhenius acid is a substance that produces H+ (H3O+) in water Arrhenius base is a substance that produces OH.

Acid/Base Definitions ‡ Definition #2: Brønsted ± Lowry Acids ± proton donor Bases ± proton acceptor A ³proton´ is really just a hydrogen atom that has lost it¶s electron! .

A Brønsted-Lowry acid is a proton donor A Brønsted-Lowry base is a proton acceptor base acid conjugate acid conjugate base .

ACIDACID-BASE THEORIES The Brønsted definition means NH3 is a BASE in water ² and water is itself an ACID NH3 Base + H 2O Acid NH4 Acid + + OH Base - .

Conjugate Pairs .

Learning Check! Label the acid.+ H3O+ . and conjugate base in each reaction: HCl + OHCl. base.+ H2O H2O + H2SO4 HSO4. conjugate acid.

a substance that donates an electron pair .a substance that accepts an electron pair Lewis base .Acids & Base Definitions Definition #3 ± Lewis Lewis acid .

Lewis Acids & Bases Formation of hydronium ion is also an excellent example. H + ‡‡ ‡ O² H ‡ H BASE H ‡‡ O² H H A C ID ‡Electron pair of the new O-H bond Ooriginates on the Lewis base. .

Lewis Acid/Base Reaction .

Acid Base Strength ‡ Arrhenius ‡ Brønsted ± Lowry ‡ Lewis .

Equilibrium aA + bB cC + dD [C]c[D]d Kc = [A]a[B]b .

The pH scale is a way of expressing the strength of acids and bases. we just use the NEGATIVE power of 10 on the Molarity of the H+ (or OH-) ion. Instead of using very small numbers. Under 7 = acid 7 = neutral Over 7 = base .

pH of Common Substances .

Calculating the pH pH = .74) pH = 4.4.(.8 X 10-5 pH = .8 X 10-5 pH = .log 1 X 10-10 pH = .log 1.74 .10) pH = 10 Example: If [H+] = 1.(.log [H+] (Remember that the [ ] mean Molarity) Example: If [H+] = 1 X 10-10 pH = .

pH = log [H+] Take antilog (10x) of both sides and get 10-pH = [H+] [H+] = 10-3.log [H+] then .12 = 7.pH calculations ² Solving for H+ If the pH of Coke is 3. [H+] = ??? Because pH = .12. look for ³Shift´ or ³2nd function´ and then the log button .6 x 10-4 M *** to find antilog on your calculator.

log [H+] -8.5 = [H+] 3.5.16 X 10-9 = [H+] .pH calculations ² Solving for H+ ‡ A solution has a pH of 8.log [H+] 8.5 = . What is the Molarity of hydrogen ions in the solution? pH = .5 = antilog (log [H+]) 10-8.5 = log [H+] Antilog -8.

More About Water H2O can function as both an ACID and a BASE. In pure water there can be AUTOIONIZATION Equilibrium constant for water = Kw Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC .

More About Water Autoionization OHH3O+ Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC In a neutral solution [H3O+] = [OH-] so Kw = [H3O+]2 = [OH-]2 and so [H3O+] = [OH-] = 1.00 x 10-7 M .

‡ pOH looks at the perspective of a base pOH = . pH and pOH are opposites! ‡ pOH does not really exist. pH + pOH = 14 . but it is useful for changing bases to pH.log [OH-] Since pH and pOH are on opposite ends.pOH ‡ Since acids and bases are opposites.

pH [H+] [OH-] pOH .

Strong and Weak Acids/Bases The strength of an acid (or base) is determined by the amount of IONIZATION. . HNO3. H2SO4 and HClO4 are among the only known strong acids. HCl.

(aq) HNO3 is about 100% dissociated in water. .Strong and Weak Acids/Bases ‡ Generally divide acids and bases into STRONG or WEAK ones. STRONG ACID: HNO3 (aq) + H2O (l) ---> ---> H3O+ (aq) + NO3.

Strong and Weak Acids/Bases ‡ Weak acids are much less than 100% ionized in water. One of the best known is acetic acid = CH3CO2H .

CaO (lime) + H2O --> --> Ca(OH)2 (slaked lime) CaO . NaOH (aq) ---> Na+ (aq) + OH.(aq) ---> Other common strong bases include KOH and Ca(OH)2.Strong and Weak Acids/Bases ‡ Strong Base: 100% dissociated in water.

(aq) .Strong and Weak Acids/Bases ‡ Weak base: less than 100% ionized in water One of the best known weak bases is ammonia NH3 (aq) + H2O (l) NH4+ (aq) + OH.

Weak Bases .

Equilibria Involving Weak Acids and Bases Consider acetic acid.8 x 10 [HOAc] Conj.] -5 Ka ! ! 1. HC2H3O2 (HOAc) HC2H3O2 + H2O H3O+ + C2H3O2 Acid [H 3 O ][OAc . base (K is designated Ka for ACID) K gives the ratio of ions (split up) to molecules (don¶t split up) .

Ionization Constants for Acids/Bases Acids Increase strength Conjugate Bases Increase strength .

7 .Equilibrium Constants for Weak Acids Weak acid has Ka < 1 Leads to small [H3O+] and a pH of 2 .

Equilibrium Constants for Weak Bases Weak base has Kb < 1 Leads to small [OH-] and a pH of 12 .7 .

[H3O+] and pH .Relation of Ka. Kb.

+ H2O Na+ + HAc + OH- Kh Kw Ka 1.5 v 10 10 .01 M solution of sodium acetate ‡ Na+ + Ac .Hydrolysis ‡ Salt of a weak acid and strong base ‡ ‡ ‡ ‡ Calculate: 1) the hydrolysis constant. 2) the degree of hydrolysis and 3) the hydrogen concentration for 0.82 v 10 5.0 v 10 14 5 1.

Hydrolysis ‡ The degree of dissociation is given by Kh x2 .

01 .5 v 10 10 x 2 v 0.1  x V ‡ Substituting for Kh and V = 1/c we obtain 5.

000235 or 0. x = 0.0235% .1  x ‡ Solving this quadratic equation.

Hydrolysis
‡ If the solution was completely hydrolysed, the concentration of acetic acid produced would be 0.01 M. But the degree of hydrolysis is 0.0235%. Therefore the concentration of acetic acid is 2.35 x 10-6 M ‡ This is also equal to the hydroxide ion concentration ‡ [OH-] = 2.35 x 10-6 ‡ M pOH = 5.63 ‡ pH = pKw ± pOH i.e. pH = 14 ± 5.63 = 8.37 ‡ The pH may also be determined using ‡ pH = ½pKw + ½pKa + ½log c ‡ = 7.0 + 2.37 + ½(-2) ‡ pH = 8.37

Hydrolysis
‡ Salt of a strong acid and weak base
‡ Determine the pH of a 0.2 M NH4Cl solution NH4OH + Cl- + H+ ‡ NH4- + Cl- + H2O

Kh

?H ANH OH A ! ?Acid Av ?BaseA ? ! 

?NH A
4

4 

Kw ! ?Unhydrolysed Salt A K b

x2 !

1 - x V
‡ Since [NH4OH] and [H+] are equal

74 ‡ pH = ½pKw .85 x 10-5 and ‡ pKb = 4.h Hydrolysis   2 ? A 4 A! ? A ! ? !  4 c b ? A!  cv b pH ! 1 p 2 1 p 2  1 log c b 2 ‡ Ammonia in water Kb = 1.½pKb .½log c .

98 .½(-0.Hydrolysis ‡ pH = ½(14) .74) .0 ± 2.6989) ‡ pH = 7.37 + 0.3495 ‡ pH = 4.½(4.

........ (1) Kh ! ?BaseA™ ?Acid A ?Hydrolysed Salt A2 ....+ H2O ‡ Kh ! Kh a NH 4OH v a HAc a NH  v a Ac  4 ?NH 4OH A™ ?HAc Av ! ?NH A™ ?Ac A   4 f NH 4OH  f HAc f NH  ™ f Ac  4 ?NH 4OH A™ ?HAcA ! ?NH A™ ?Ac A   4 ..Hydrolysis ‡ Salt of a weak acid and weak base NH4OH + HAc ‡ NH4+ + Ac......

[M+] = [A-] = (1 ± x)/V ‡ Substituting the values in the equation 1 given in the previous slide x Kh ! . then ‡ [MOH] = [HA] = x/V. of salt dissolved in V litres of solution.Hydrolysis ‡ If x is the degree of hydrolysis of 1g mol.

1  x ™x ™ .

 x 1 x ! 2 .

.x 1 2 ‡ The degree of hydrolysis and consequently pH is independent of the concentration of the solution.

it can be shown that Kh ! K K a v Kb pK h ! pK  pK a  pK b .Hydrolysis ‡ Remembering the following equations must hold simultaneously K w ! H  v OH    Ka ? A? A ?H Av ?Ac Aand K ! ? A ? A NH v OH !   4 ?HAc A b NH 4OH ‡ Also.

?H A! K ?A A  a  ?HAA ! K v x av .Hydrolysis ‡ The hydrogen ion concentration of the hydrolysed solution is calculated in the following manner.

1  x x ! Ka v .

1  x but x .

 x ! K h 1 ?H A! K  a ™ K h ! K v K a Kb or pH ! 1 pK  1 pK a  1 pK b 2 2 2 .

0 +1.Hydrolysis ‡ If the ionisation constant of the acid and base are equal.37 ± 2. ‡ Ka > Kb.77 x 10-4. pKa = 3.88 ± 2. although the hydrolysis may be considerable.37 = 6. pH > 7 ‡ The pH of a solution of ammonium acetate is given by: ‡ pH = 7. Ka = 1.0 and the solution is approximately neutral ‡ On the other hand. pH < 7 ‡ Kb > Kc.75 and the solution reacts slightly acid. i. Ka = Kb. for a solution of ammonium formate ‡ pH = 7.0 + 2.e.51 ‡ Formic acid. .37 = 7. pH = ½pKw = 7 and the solution is neutral.

an aqueous solution of NH4Ac pH = 7 ‡ The addition of 1 mL of 1M HCl to 1 litre of KCl changes the pH to § 3 ‡ The addition of 1 mL of 1M HCl to 1 litre of NH4Ac does not change the pH much at all.0001 M HCl should have a pH of 4. ‡ An aqueous solution of KCl pH = 7 ‡ Likewise. ‡ Likewise a solution of 0.pH Buffers ‡ A solution of 0. but this solution is extremly sensitive to traces of alkali from the glass container and ammonia in the air.0001 M NaOH should have a pH of 10 but this solution is sensitive to carbon dioxide in the air. .

.pH Buffers ‡ This is because the H+ ions added are mopped up by the acetate ions: H+ + AcHAc (the equilibrium lies very much to the right hand side of this equation). A buffer possesses reserved acidity and reserved alkalinity. ‡ The ammonium acetate it is behaving as a buffer and resisting changes in pH.

HA H+ + A‡ Making an approximation of activities § concentrations ?H  ?HAAv K A! ?A A  a ‡ If the concentration of the acid = ca ‡ The concentration of the salt = cs ‡ Then the concentration of the un-dissociated portion of the acid = ca ± [H+] ‡ The solution must be electrically neutral [A-] = cs + [H+] .pH Buffers ‡ For a buffer formed from a weak acid (HA) and the salt of a weak acid (MA).

the dissociation constant of the acid is repressed by the common ion effect.pH Buffers ?H A  ca  H  ! v Ka  cs  H ? A ? A ‡ The quadratic equation can be solved for [H+] ‡ It can also be simplified by considering that in a mixture of weak acid with its salt. The hydrogen ion concentration is negligibly small in comparison with ca and cs ‡ Equation reduces to: ?H A  ca ! ™ Ka cs ?H  ?AcidA™ K A! ?Salt A a .

74 ‡ At half titre point a 0.g 1. This would also be true for higher and lower concentrations of HAc.74.e.0 M and 0.pH Buffers ‡ Or ?Salt A pH ! pK a  log ?AcidA Similarly ?BaseAv K ?OH A! ?Salt A b - or p ?Salt A H ! pK b  log ?BaseA ‡ If the concentrations of an acid and salt are equal (i.05 M HAc . pKa = 4. Ka = 1. half neutralised).1 M HAc solution would have a pH of 4.82 x 10-5. e. then pH = pKa ‡ For acetic acid.

More acetic will dissociate to replace the H+ ions depleted in this manner. ‡ Example: Calculate the pH of a solution produced by adding 10 mL of 1M HCl to 1 liter of a solution which is 0.pH Buffers ‡ If we add a small concentration of H+ ions they would combine with acetate ions to form acetic acid.1M in sodium acetate.1M in acetic acid and 0. ‡ The pH of the acetic acid ± sodium acetate buffer is given by: .added will combine with H+ ions from dissociation of HAc and form water. ‡ H+ + CH3COOCH3COOH ‡ Similarly a small concentration of OH.

‡ The HCl reacts with acetate ion forming pratically undissociated acetic acid.00 ! 4.1 + 0.11 ‡ pH = 4.0.09 = 4.pH Buffers ?Salt A ! 4.01 = 0.01 = 0.09 ‡ And [CH3COOH] = 0.1.74 pH ! pK a  log ?AcidA ‡ Neglecting the volume change from 1000 to 1010 mL. ‡ H+ + CH3COOCH3COOH ‡ Therefore [CH3COO-] = 0.74  0.65 .09/0.74 + log 0.74 ± 0.11 = 4.

74 . but the pH will differ slightly from the half-neutralized acid.09 pH ‡ Adding 10 mL of 1M HCl to 1 litre of pure water (pH 7). ‡ A solution that contains equal concentrations of acid and salt.pH Buffers ‡ The addition of the strong acid to the buffer change the pH by 4. ‡ E. by 5 pH unites. a quarter neutralized solution of acid.01) = 2. [Acid] = 3[Salt] ‡ pH = pKa + log ‡ = pKa ± 0. the pH would have changed from 7 to ±log(0. Other mixtures will also have considerable buffer capacity. or a half neutralized solution.477 .65 = 0.4.g. has the maximum buffer capacity.

477 ‡ Generally speaking the buffering capacity is maintained for mixtures within the range: ‡ 1 acid : 10 salt and 10 acid : 1 salt ‡ pH = pKa s 1 ‡ The concentration of the acid is usually of the order 0.20 M. a three quarter neutralized acid solution. 3[Acid] = [Salt] ‡ pH = pKa + log 3 ‡ = pKa + 0.g.050. ‡ Similar remarks apply to buffers of weak bases (NH3/NH4Cl) .pH Buffers ‡ E.