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Chapter 16 Acid-Base Equilibria
Chapter 16 Acid-Base Equilibria
16 – Acid‐Base Equilibria
16.1 Acids & Bases: A Brief Review
‐ Arrhenius acids and bases:
‐‐ acid: an H+ donor HA(aq) H(aq) A (aq)
‐‐ base: an OH‐ donor MOH (aq) M (aq) OH(aq)
‐ Brønsted‐Lowry acids and bases:
‐‐ acid: an H+ donor HA(aq) H(aq) A (aq)
‐‐ base: an H+ acceptor H (aq) B(aq) BH (aq)
16.2 Brønsted‐Lowry Acids & Bases
‐ The H+ Ion in Water
‐‐ H 3O is called the hydronium ion and is what truly happens when H+ is in water
‐‐ since all aqueous solution are in water we will use H3O+ & H+ interchangeably
‐ Conjugate Acid‐Base Pairs
‐‐ conjugate acid: the acid that is created after the Brønsted‐Lowry base has accepted the proton, BH+
‐‐ conjugate base: the base that is created after the Brønsted‐Lowry acid has donated the proton, A‐
‐‐ examples:
basic: NH 3( g ) H 2 O(l ) NH 4( aq ) OH ( aq ) K b 1.76 105
base acid conj acid conj base
HCl H 2O Cl
acidic: H 3O K a 1
acid baseconj base conj acid
‐ Relative Strengths of Acids & Bases
‐‐ a strong acid will completely dissociate/ionize in solution:
HNO3( aq ) H 2O(l ) H 3O(aq ) NO3( aq )
‐‐‐ as soon as a strong acid is placed in water it will ionize completely
‐‐‐‐ all the reactant goes to product
‐‐‐‐ product is a very weak conjugate acid and base
‐‐‐ other strong acids: HCl, HBr, H2SO4, HI, HClO4, HClO3, HNO3
‐‐ the same is the case for a strong base
‐‐‐ examples of strong bases: MOH (where M is alkali metal), NH 2 , H‐
‐‐ a weak acid will only partially dissociate
HNO2( aq ) H (aq ) NO2( aq ) K a 4.0 104
‐‐‐ the eq constant is called Ka “a” for acid
‐‐‐ in this case some of the reactant is present at eq
‐‐ the larger the Ka the more an acid dissociates, the stronger the acid
‐‐‐ e.g. for nitric acid Ka >> 1
‐‐ we talk about Ka's at length a little later
16.3 The Autoionization of Water
‐ as we will soon learn water may act as either an acid or a base ‐ amphoteric
‐‐ water as a base: HA (aq) H 2 O(l) H3O(aq) A (aq)
‐‐ water as an acid: B(aq) H 2 O(l) BH (aq) OH (aq)
‐ Autoionization occurs when a species can ionize itself this occurs for water as shown below:
2 H 2O(l ) OH (aq ) H 3O(aq ) K c [OH (aq ) ][ H 3O(aq ) ]
‐ since water is in excess (it’s the solvent) the concentration is constant
K w [OH (aq ) ][ H 3O(aq ) ]
‐ relationship between [OH (aq ) ] and [ H 3O(aq ) ]
[ H 3O(aq ) ] [OH (aq ) ] acidic
[ H 3O(aq ) ] [OH (aq ) ] neutral
[ H 3O(aq ) ] [OH (aq ) ] basic
‐ the value for both [OH (aq ) ] and [ H 3O(aq ) ] in pure water are 1.0 x 10‐7 at 298K
K w (1.0 10 7 )(1.0 10 7 ) 1.0 10 14
‐ Example: Determine the hydroxide concentration in a solution with
[ H 3O(aq ) ] 1.89 104 M .
Kw 1.0 1014
K w [ H 3O(aq ) ][OH (aq ) ] [OH (aq ) ] 5.29 1011 M
[ H 3O(aq ) ] 1.89 104
16.4 The pH Scale
‐ pH is a log scale which describes the "power of hydrogen"
‐ the pH is related to the [ H 3O(aq ) ] : pH log[ H 3O(aq ) ]
‐‐ for pure water: pH log[ H 3O(aq ) ] log(1.0 107 ) 7 this is neutral pH
‐‐ when a solution has a pH < 7.0 it is acidic
‐‐ when a solution has a pH > 7.0 it is basic
‐ pOH & Other ‘p’ Scales
‐‐ all ‘p’ scales mean ‘‐log’ of
‐‐ pOH is exactly like pH except it is dependent upon [OH (aq ) ] : pOH = ‐log [OH (aq ) ]
‐‐ In Chapter 17 we will have pKa and pKb meaning the –log(Ka) etc.
‐‐ the pH and pOH are related to Kw
K w [OH (aq ) ][ H 3O(aq ) ]
log K w log{[OH (aq ) ][ H 3O(aq ) ]}
log K w log[OH (aq ) ] log[ H 3O(aq ) ]
pK w pOH pH log(1.0 1014 ) 14
‐ Measuring pH
‐‐ you may have used a litmus paper in GenChem I lab to see if something was more or less basic
‐‐‐ phenolphthalein is pink in basic solution and appears clear in acidic as you can see above
‐‐ This will become more relevant in Chapter 17 when we talk about titrations when we talk about color
indicators
16.5 Strong Acids & Bases
‐ as we previously discussed strong acids and bases completely dissociate in water
‐‐ therefore, whatever the concentration of our strong acid or base will be the
concentration of the H+ and OH‐, respectively
‐ Examples: Write the balanced equation for each of the following and determine the
pH.
a.) 0.5000 M HClO4(aq)
HClO 4(aq) H 2 O(l) H 3 O(aq) ClO 4(aq)
[H 3 O(aq) ] [HClO 4(aq) ] 0.5000 M
pH log(0.5000 M) 0.30
b.) 0.0256 M LiOH(aq)
LiOH (aq) Li (aq) OH (aq)
[OH (aq) ] [LiOH (aq) ] 0.0256 M
pH 14 pOH 14 ( log(0.0256 M)) 12.41
‐ Example: Determine the hydronium ion concentration for a 0.01500 M Ca(OH)2.
2
Ca(OH) 2(aq) Ca (aq) 2OH (aq)
OH (aq)
2 Ca(OH) 2(aq) 2 0.01500 M 0.03000 M
Kw 1.0 1014
[H 3 O(aq) ] 3.33 1013 M
OH (aq)
0.03000 M
16.6 Weak Acids
‐ weak acids and bases do not completely dissociate in water ‐ therefore at eq they are still present:
HA( aq ) H 2 O(l ) H 3O(aq ) A(aq ) or HA( aq ) H (aq ) A(aq )
H 3O(aq ) A(aq ) H (aq ) A(aq )
Ka
HA HA
‐ the Ka is called the acid‐dissociation constant and gives us an idea of acid strength
‐‐ the larger the Ka the more strongly the equilibrium will lie toward product
‐‐ the more likely the acid is to dissociate and raise the acidity of the solution
‐‐ the stronger the acid
‐ Calculating Ka from pH
‐‐ Similar to what we did last chapter with the %dissociation, we can get the Ka from the pH
‐‐ Example: What is the Ka of a 0.050 M solution of HC7H5O2 if the pH of this solution is 2.75?
HC7 H 5O2( aq ) C7 H 5O2( aq ) H (aq )
We begin with an ICE Table
x
2
2
0.062 7.90 10
x x 8.51 103 M
2
[H+] = 0.050+0.0085 = 0.059M
‐‐ Why is Ka1 > Ka2?
H 2 SO4( aq ) H (aq ) HSO4( aq ) K a 1
2
HSO 4( aq ) H ( aq ) SO4( aq ) K a 1.2 102
‐‐ electrostatically, it is more difficult to remove H+ from SO4(2aq ) than HSO4( aq )
‐‐ therefore, the second Ka is always smaller than the first
16.7 Weak Bases
‐‐ we handle them just like we do weak acids
‐ this time our eq const is the base dissociation constant or Kb
‐ Example: Calculate the pH of 0.050 M NH3.
NH 3( aq ) H 2 O OH (aq ) NH 4( aq ) Kb 1.8 105
NH 3( aq ) OH (aq ) NH 4( aq )
Initial 0.050 0.0 0.0
Change ‐x +x +x
Eq 0.050 ‐ x +x +x
[OH (aq ) ][ NH 4( aq ) ] x2
Ka 1.8 105
[ NH 3( aq ) ] 0.050 x
x 2 9 107 1.8 105 x x 2 1.8 105 x 9 107 0