ACID BASE CHEMISTRY

Acid and Bases

Acid and Bases

Acid and Bases

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

Bases
Have a bitter taste. Feel slippery. 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 Blue to Red A-CID

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

Some Properties of Bases

Produce OH- ions in water Taste bitter, chalky Are electrolytes Feel soapy, slippery React with acids to form salts and water pH greater than 7 Turns red litmus paper to blue Basic Blue

Some Common Bases

NaOH KOH Ba(OH)2 sodium hydroxide caustic soda potassium hydroxide liquid soap

barium hydroxide stabilizer for plastics MOM Milk of

Mg(OH)2 magnesium hydroxide magnesia Al(OH)3 aluminum hydroxide

Maalox (antacid)

Acid/Base definitions
Definition #1: Arrhenius (traditional) Acids produce H+ ions (or hydronium ions H3O+) Bases produce OH- ions (problem: some bases dont have hydroxide ions!)

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

Arrhenius base is a substance that produces OH- in water

Acid/Base Definitions
Definition #2: Brnsted Lowry Acids proton donor Bases proton acceptor A proton is really just a hydrogen atom that has lost its electron!

A Brnsted-Lowry acid is a proton donor A Brnsted-Lowry base is a proton acceptor

base

acid

conjugate acid

conjugate base

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

+ OH Base

Conjugate Pairs

Learning Check!
Label the acid, base, conjugate acid, and conjugate base in each reaction: HCl + OHCl- + H2O

H2O + H2SO4

HSO4- + H3O+

Acids & Base Definitions

Definition #3 Lewis Lewis acid - a substance that accepts an electron pair
Lewis base - a substance that donates an electron pair

Lewis Acids & Bases

Formation of hydronium ion is also an excellent example.
H
+

O H H BASE

O 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 Brnsted 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. Instead of using very small numbers, we just use the NEGATIVE power of 10 on the Molarity of the H+ (or OH-) ion. Under 7 = acid 7 = neutral Over 7 = base

pH of Common Substances

Calculating the pH
pH = - log [H+]
(Remember that the [ ] mean Molarity) Example: If [H+] = 1 X 10-10 pH = - log 1 X 10-10 pH = - (- 10) pH = 10 Example: If [H+] = 1.8 X 10-5 pH = - log 1.8 X 10-5 pH = - (- 4.74) pH = 4.74

pH calculations Solving for H+

If the pH of Coke is 3.12, [H+] = ??? Because pH = - log [H+] then - pH = log [H+] Take antilog (10x) of both sides and get

10-pH = [H+]
[H+] = 10-3.12 = 7.6 x 10-4 M
*** to find antilog on your calculator, look for Shift or 2nd function and then the log button

pH calculations Solving for H+

A solution has a pH of 8.5. What is the Molarity of hydrogen ions in the solution?
pH = - log [H+] 8.5 = - log [H+] -8.5 = log [H+] Antilog -8.5 = antilog (log [H+]) 10-8.5 = [H+] 3.16 X 10-9 = [H+]

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

pH + pOH = 14

pH

[H+]

[OH-]

pOH

Strong and Weak Acids/Bases

The strength of an acid (or base) is determined by the amount of IONIZATION.

HNO3, HCl, H2SO4 and HClO4 are among the only known strong acids.

Strong and Weak Acids/Bases

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

Strong and Weak Acids/Bases

Weak acids are much less than 100% ionized in water. One of the best known is acetic acid = CH3CO2H

Strong and Weak Acids/Bases Strong Base: 100% dissociated in water.

NaOH (aq) ---> Na+ (aq) + OH- (aq) --->
Other common strong bases include KOH and Ca(OH)2. CaO (lime) + H2O --> --> Ca(OH)2 (slaked lime) CaO

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- (aq)

Weak Bases

Equilibria Involving Weak Acids and Bases

Consider acetic acid, HC2H3O2 (HOAc) HC2H3O2 + H2O H3O+ + C2H3O2 Acid
[H 3 O ][OAc - ] -5 Ka ! ! 1.8 x 10 [HOAc]

Conj. base

(K is designated Ka for ACID) K gives the ratio of ions (split up) to molecules (dont split up)

Ionization Constants for Acids/Bases

Acids
Increase strength

Conjugate Bases

Increase strength

Equilibrium Constants for Weak Acids

Weak acid has Ka < 1 Leads to small [H3O+] and a pH of 2 - 7

Equilibrium Constants for Weak Bases

Weak base has Kb < 1 Leads to small [OH-] and a pH of 12 - 7

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

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 0.01 M solution of sodium acetate Na+ + Ac - + H2O Na+ + HAc + OH-

Kh

Kw Ka

1.0 v 10 14 5 1.82 v 10

5.5 v 10

10

Hydrolysis
The degree of dissociation is given by

Kh

x2 1  x V

Substituting for Kh and V = 1/c we obtain

5.5 v 10

10

x 2 v 0.01 1  x

Solving this quadratic equation, x = 0.000235 or 0.0235%

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 = pKw + pKa + log c = 7.0 + 2.37 + (-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

Hydrolysis   2 ? A 4 A! ? A ! ? !
 4

? A!


cv
b

pH ! 1 p 2

1 p 2

 1 log c b 2

Ammonia in water Kb = 1.85 x 10-5 and pKb = 4.74 pH = pKw - pKb - log c

Hydrolysis
pH = (14) - (4.74) - (-0.6989) pH = 7.0 2.37 + 0.3495 pH = 4.98

Hydrolysis
Salt of a weak acid and weak base NH4OH + HAc NH4+ + Ac- + 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

.................. (1)

Kh !

?BaseA ?Acid A

?Hydrolysed Salt A2

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

x Kh ! 1  x

x   x 1

x ! 2 x 1

The degree of hydrolysis and consequently pH is independent of the concentration of the solution.

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

NH 4OH

Also, it can be shown that

Kh ! K

K a v Kb

pK h ! pK  pK a  pK b

Hydrolysis
The hydrogen ion concentration of the hydrolysed solution is calculated in the following manner.

?H A! K ?A A
 a 

?HAA ! K v

x av 1  x

x ! Ka v 1  x

but x   x ! K h 1

?H A! K


K h ! K v K a Kb

or pH ! 1 pK  1 pK a  1 pK b 2 2 2

Hydrolysis
If the ionisation constant of the acid and base are equal, i.e. Ka = Kb, pH = pKw = 7 and the solution is neutral, although the hydrolysis may be considerable. Ka > Kb, pH < 7 Kb > Kc, pH > 7 The pH of a solution of ammonium acetate is given by: pH = 7.0 + 2.37 2.37 = 7.0 and the solution is approximately neutral On the other hand, for a solution of ammonium formate pH = 7.0 +1.88 2.37 = 6.51 Formic acid; Ka = 1.77 x 10-4; pKa = 3.75 and the solution reacts slightly acid.

pH Buffers
A solution of 0.0001 M HCl should have a pH of 4, but this solution is extremly sensitive to traces of alkali from the glass container and ammonia in the air. Likewise a solution of 0.0001 M NaOH should have a pH of 10 but this solution is sensitive to carbon dioxide in the air. An aqueous solution of KCl pH = 7 Likewise, 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.

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). The ammonium acetate it is behaving as a buffer and resisting changes in pH. A buffer possesses reserved acidity and reserved alkalinity.

pH Buffers
For a buffer formed from a weak acid (HA) and the salt of a weak acid (MA). HA H+ + A Making an approximation of activities concentrations

?H

?HAAv K 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

?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 dissociation constant of the acid is repressed by the common ion effect. 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

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.e. half neutralised), then pH = pKa For acetic acid, Ka = 1.82 x 10-5, pKa = 4.74 At half titre point a 0.1 M HAc solution would have a pH of 4.74. This would also be true for higher and lower concentrations of HAc, e.g 1.0 M and 0.05 M HAc

pH Buffers
If we add a small concentration of H+ ions they would combine with acetate ions to form acetic acid. H+ + CH3COOCH3COOH Similarly a small concentration of OH- added will combine with H+ ions from dissociation of HAc and form water. 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 0.1M in acetic acid and 0.1M in sodium acetate. The pH of the acetic acid sodium acetate buffer is given by:

pH Buffers

?Salt A ! 4.74  0.00 ! 4.74 pH ! pK a  log ?AcidA

Neglecting the volume change from 1000 to 1010 mL. The HCl reacts with acetate ion forming pratically undissociated acetic acid. H+ + CH3COOCH3COOH Therefore [CH3COO-] = 0.1- 0.01 = 0.09 And [CH3COOH] = 0.1 + 0.01 = 0.11 pH = 4.74 + log 0.09/0.11 = 4.74 0.09 = 4.65

pH Buffers
The addition of the strong acid to the buffer change the pH by 4.74 - 4.65 = 0.09 pH Adding 10 mL of 1M HCl to 1 litre of pure water (pH 7), the pH would have changed from 7 to log(0.01) = 2, by 5 pH unites. A solution that contains equal concentrations of acid and salt, or a half neutralized solution, has the maximum buffer capacity. Other mixtures will also have considerable buffer capacity, but the pH will differ slightly from the half-neutralized acid. E.g. a quarter neutralized solution of acid, [Acid] = 3[Salt] pH = pKa + log = pKa 0.477

pH Buffers
E.g. a three quarter neutralized acid solution, 3[Acid] = [Salt] pH = pKa + log 3 = pKa + 0.477 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 0.050.20 M. Similar remarks apply to buffers of weak bases (NH3/NH4Cl)