Title: * * * * * * * * * * * * * * * * * * * * * * * * * * * * *
1Chapter 16. Acid Base Equilibria
2Equilibria in Solutions of Weak Acids
- The dissociation of a weak acid is an equilibrium
situation with an equilibrium constant, called
the acid dissociation constant, Ka based on the
equation - HA (aq) H2O (l) ? H3O (aq) A- (aq)
3Equilibria in Solutions of Weak Acids
- The acid dissociation constant, Ka is always
based on the reaction of one mole of the weak
acid with water. - If you see the symbol Ka, it always refers to a
balanced equation of the form - HA (aq) H2O (l) ? H3O (aq) A- (aq)
4Problem
- The pH of 0.10 mol/L HOCl is 4.23. Calculate Ka
for hypochlorous acid. - HOCl (aq) H2O (l) ? H3O (aq) ClO- (aq)
5Calculating Equilibrium Concentrations in
Solutions of Weak Acids
- We can calculate equilibrium concentrations of
reactants and products in weak acid dissociation
reactions with known values for Ka. - To do this, we will often use the ICE table
technique we saw in the last chapter on
equilibrium.
6Calculating Equilibrium Concentrations in
Solutions of Weak Acids
- We need to figure out what is an acid and what is
a base in our system. - For example, if we start with 0.10 mol/L HCN,
then HCN is an acid, and water is a base. - HCN (aq) H2O (l) ? H3O (aq) CN- (aq)
- Ka 4.9 x 10-10
7- Like our previous equilibrium problems, we then
create a table of the initial concentrations of
all chemicals, the change in their concentration,
and their equilibrium concentrations in terms of
known and unknown values. -
8-
- We can ALWAYS solve this equation using the
quadratic formula and get the right answer, but
it might be possible to do it more simply.
9- Every time we do an weak acid equilibrium
problem, divide the initial concentration of the
acid by Ka. - For this example
- 0.10 / 4.9 x 10-10 2 x 108
10- 0.10 / 4.9 x 10-10 2 x 108
- Since this value is greater than 100, we can
assume that the initial concentration of the acid
and the equilibrium concentration of the acid are
the same. - This assumption will lead to answers with less
than 5 error since this pre-check is greater
than 100.
11- The assumption we will make is that
- x ltlt HCNi so HCNeqm ? HCNI
- 4.9 x 10-10 x2 / 0.10
- x2 (4.9 x 10-10)(0.10)
- x ?4.9 x 10-11
- x ?7.0 x 10-6 mol/L
12- Based on the assumption weve made, at
equilibrium - x H3Oeqm CN-eqm
- 7.0 x 10-6 mol/L
- (-ve value isnt physically possible)
- HCNeqm 0.10 mol/L.
13.
- Any time we make an assumption,
- we MUST check it.
- We assumed x ltlt HCNi
- To check the assumption, we divide x by HCNi
and express it as a percentage
14- As long as the assumption check is less than 5,
then - the assumption is valid!
- If the assumption was not valid, we would have to
go back and use the quadratic formula!
15Remember!
- H2O (l) H2O (l) ? H3O (aq) OH- (aq)
- is always taking place in water whether or not we
have added an acid or base. - This reaction also contributes
- H3O (aq) and OH- (aq)
- to our system at equilibrium
16Remember!
- Since at 25 ?C
- Kw H3O OH- 1.0 x 10-14
- it turns out that if our acid-base equilibrium
were interested in gives a pH value between
about 6.8 and 7.2 then the auto-dissociation of
water contributes a significant amount of H3O
and OH- to our system and the real pH would not
be what we calculated in the problem.
17Problem
- Acetic acid CH3COOH (or HAc) is the solute that
gives vinegar its characteristic odour and sour
taste. Calculate the pH and the concentration of
all species present in - a) 1.00 mol/L CH3COOH
- b) 0.00100 mol/L CH3COOH
18Problem a)
Lets check the initial acid concentration / Ka
ratio. 1.00 / 1.8 x 10-5 ? 55000 is larger
than 100.
19Problem a)
We can probably assume that x ltlt HAci so
HAceqm ? HAci 1.8 x 10-5 x2 / 1.00 x2
(1.8 x 10-5)(1.00) x ?1.8 x 10-5 x ?4.2 x
10-3 mol/L (but must be value since x H3O)
20Problem a)
- So at equilibrium,
- H3O CH3COO- 4.2 x 10-3 mol/L
- CH3COOH 1.00 mol/L.
-
-
- The assumption was valid and so
- pH - log H3O
- pH - log 4.2 x 10-3
- pH 2.38
21Problem b)
Lets check the initial acid concentration / Ka
ratio. 0.00100 / 1.8 x 10-5 ? 56 is smaller
than 100.
22Problem b)
We can probably CAN NOT assume that x ltlt HAci
so HAceqm ? HAci
23Problem b)
24Problem b)
Since H3O x we must use the positive value,
so H3O CH3COO- 1.3 x 10-4
mol/L CH3COOH 0.00100 mol/L 1.3 x 10-4
mol/L 0.00087 mol/L.
25Problem b)
Lets confirm that x ltlt HAci IS NOT TRUE pH
- log H3O pH - log 4.2 x 10-4 pH 3.38
26Problem
- A vitamin C tablet containing 250 mg of ascorbic
acid (C6H8O6 Ka 8.0 x 10-5 is dissolved in a
250 mL glass of water to give a solution where
C6H8O6 5.68 x 10-3 mol/L. - What is the pH of the solution?
27Problem
- Check the initial acid concentration / Ka ratio.
- 5.68 x 10-3/ 8.0 x 10-5 ? 71
- which is not larger than 100 so
28Problem
29Problem
- Since H3O x the answer must be the positive
value - H3O C6H7O6- 6.3 x 10-4 mol/L
- C6H8O6 (5.68 x 10-3 - 6.3 x 10-4) mol/L
- 5.05 x 10-3 mol/L
- pH - log H3O
- pH - log 6.3 x 10-4
- pH 3.20
30Degree of ionization
- The pH of a solution of a weak acid like acetic
acid will depend on the initial concentration of
the weak acid and Ka. Therefore, we can define a
second measure of the strength of a weak acid by
looking of the - degree (or percent) ionization of the acid.
-
- ionization HAionized / HAinitial x 100
31Percent ionization
- In part a) of an earlier problem an acetic acid
solution with initial concentration of 1.00 mol/L
at equilibrium had - H3Oeqm HAionized 4.2 x 10-3 mol/L
- ionization HAionized / HAinitial x 100
- ionization 4.2 x 10-3 mol/L / 1.00 mol/L x
100 - ionized 0.42
32Percent ionization
- In part b) of an earlier problem an acetic acid
solution with initial concentration of 0.00100
mol/L at equilibrium had - H3O HAionized 1.3 x 10-4 mol/L
- ionization HAionized / HAinitial x 100
- ionization 1.3 x 10-4 mol/L / 0.00100 mol/L x
100 - ionization 13
33Figure
34Equilibria in Solutions of Weak Bases
- The dissociation of a weak base is an equilibrium
situation with an equilibrium constant, called
the base dissociation constant, Kb based on the
equation - B (aq) H2O (l) ? BH (aq) OH- (aq)
35Equilibria in Solutions of Weak Bases
- The base dissociation constant, Kb is always
based on the reaction of one mole of the weak
base with water. - If you see the symbol Kb, it always refers to a
balanced equation of the form - B (aq) H2O (l) ? BH (aq) OH- (aq)
36Equilibria in Solutions of Weak Bases
- Our approach to solving equilibria problems
involving bases is exactly the same as for acids. - 1. Set up the ICE table
- 2. Establish the equilibrium constant
expression - 3. Make a simplifying assumption when possible
- 4. Solve for x, and then for eqm amounts
37Problem
- Strychnine (C21H22N2O2), a deadly poison used for
killing rodents, is a weak base having Kb 1.8 x
10-6. Calculate the pH if - C21H22N2O2initial 4.8 x 10-4 mol/L
38Problem
Check the initial base concentration / Kb ratio
4.8 x 10-4 / 1.8 x 10-6 ? 267 which is
greater than 100 We are probably good to make a
simplifying assumption that x ltlt C21H22N2O2i
39- The assumption we will make is that
- x ltlt C21H22N2O2i so
- C21H22N2O2eqm ? C21H22N2O2I
- 1.8 x 10-6 x2 / 4.8 x 10-4
- x2 (1.8 x 10-6)(4.8 x 10-4)
- x ?8.64 x 10-10
- x ?2.94 x 10-5 mol/L
40Problem
- Since x OH-, the answer must be the positive
value, - x C21H23N2O2 OH- 2.9 x 10-5 mol/L
- C21H22N2O2 4.8 x 10-4 mol/L 2.9 x 10-5
mol/L - 4.5 x 10-4 mol/L.
- We should check the assumption!
41Problem
- In this case, the error is more than 5.
- I will leave it to you to go back and use the
quadratic formula. - Compare the two answers
42Problem
- To continue towards the answer of the problem AS
IF the assumption WERE VALID - pOH - log OH-
- pOH - log 2.9 x 10-5
- pOH 4.54
- pH pOH 14.00
- pH 14.00 - pOH
- pH 14.00 - (4.54)
- pH 9.46
43Relation Between Ka and Kb
- The strength of an acid in water is expressed
through Ka, while the strength of a base can be
expressed through Kb - Since Brønsted-Lowry acid-base reactions involve
conjugate acid-base pairs there should be a
connection between the - Ka value and the Kb value of a
- conjugate acid-base pair.
44Relation Between Ka and Kb
- HA (aq) H2O (l) ? H3O (aq) A- (aq)
- A- (aq) H2O (l) ? OH- (aq) HA (aq)
45- Since these reactions take place in the same
beaker at the same time lets - add them together
46- The sum of the reactions is the dissociation of
water reaction, which has the ion-product
constant for water - Kw H3O OH- 1.0 x 10-14 at 25 C
- Closer inspection shows us that
47- As the strength of an acid increases (larger Ka)
the strength of the conjugate base must decrease
(smaller Kb) because their product must always be
the dissociation constant for water Kw.
48- Strong acids always have very weak conjugate
bases. Strong bases always have very weak
conjugate acids. - Since Ka x Kb Kw
- then Ka Kw / Kb
- and Kb Kw / Ka
49Problem
- a) Piperidine (C5H11N) is an amine found in
black pepper. Find Kb for piperidine in Appendix
C, and then calculate Ka for the C5H11NH cation. - Kb 1.3 x 10-3
- b) Find Ka for HOCl in Appendix C, and then
calculate Kb for OCl-. - Ka 3.5 x 10-8
50Acid-Base Properties of Salts
- When acids and bases react with each other,
- they form ionic compounds called salts.
- Salts, when dissolved in water, can lead to
acidic, basic, or neutral solutions, depending on
the relative strengths of the acid and base we
derive them from. - Strong acid Strong base ? Neutral salt solution
- Strong acid Weak base ? Acidic salt solution
- Weak acid Strong base ? Basic salt solution
51Salts that Yield Neutral Solutions
- Strong acids and strong bases react to form
neutral salt solutions. When the salt
dissociates in water, the cation and anion do not
appreciably react with water to form H3O or OH-.
52Salts that Yield Neutral Solutions
- Strong base cations like the alkali metal cations
(Li, Na, K) or alkaline earth cations (Ca2,
Sr2, Ba2, but NOT Be2) and strong acid anions
such as Cl-, Br-, I-, NO3-, and ClO4- will
combine together to give neutral salt solutions
with pH 7.
53Salts that Yield Neutral Solutions
- Sodium chloride (NaCl) will dissociate into Na
and Cl- in water. - Cl- has no acidic or basic tendencies.
- Cl- (aq) H2O (l) ? no reaction
- Chloride ions DO NOT HAVE hydrolysis reactions
with water since it is the conjugate of a
strong acid, which makes it very, very weak.
54Salts that Yield Neutral Solutions
- Na has no acidic or basic tendencies.
- Na (aq) H2O (l) ? no reaction
- Sodium ions DO NOT HAVE hydrolysis reactions with
water since it is the conjugate of a strong
base, which makes it very, very weak.
55Salts that Yield Acidic Solutions
- The reaction of a strong acid with anions like
- Cl-, Br-, I-, NO3-, and ClO4-
- with a weak base will lead to an
- acidic salt solution.
- The solution is acidic because the anion shows no
acidic or basic tendencies, but the cation does,
as it is the conjugate acid of a weak base.
56Salts that Yield Acidic Solutions
- Ammonium chloride (NH4Cl) will dissociate into
NH4 and Cl- in water. - Cl- has no acidic or basic tendencies.
- Cl- (aq) H2O (l) ? no reaction
- Chloride ions DO NOT HAVE hydrolysis reactions
with water since it is the conjugate of a
strong acid, which makes it very, very weak.
57Salts that Yield Acidic Solutions
- NH4 has acidic tendencies.
- That is
- NH4 (aq) H2O (l)? NH3 (aq) H3O (aq)
- Ammonium ions hydrolyze in water because it is
the conjugate acid of the weak base NH3, which
means ammonium is a weak acid.
58Salts that Yield Basic Solutions
- The reaction of a strong base with cations like
Li, Na, K, Ca2, Sr2, and Ba2 - with a weak acid will lead to an
- basic salt solution.
- The solution is acidic because the cation shows
no acidic or basic tendencies, but the anion
does, as it is the conjugate base of a weak acid.
59Salts that Yield Basic Solutions
- Sodium fluoride (NaF) will dissociate into Na
and F- in water. - Na (aq) H2O (l) ? no reaction
- Sodium ions DO NOT HAVE hydrolysis reactions with
water since it is the conjugate of a strong
base, which makes it very, very weak.
60Salts that Yield Basic Solutions
- F- has basic tendencies.
- That is
- F- (aq) H2O (l)? HF (aq) OH- (aq)
- Fluoride ions hydrolyze in water because it is
the conjugate base of the weak acid HF, which
means fluoride is a weak base.
61Problem
- Predict whether the following salt solution is
neutral, acidic, or basic and calculate the pH. - 0.25 mol/L NH4Br NH3 has a Kb value of 1.8 x
10-5
62Problem
Initial acid HA / Ka ratio is 0.25 / 5.56 x
10-10 ? 4.5 x 108 we can probably assume 0.25 gtgt
x 5.56 x 10-10 x2 / 0.25 x2 (5.56 x
10-10)(0.25) x2 1.39 x 10-10 x ?1.39 x
10-10 x 1.18 x 10-5 mol/L
63Problem
Negative answer not physically possible
so therefore, H3O 1.18 x 10-5 mol/L Since
weve shown the assumption is valid pH -log
H3O - log 1.18 x 10-5 4.93.
64Salts that Contain Acidic Cations and Basic
Anions
- If a salt is composed of an
- acidic cation
- and a
- basic anion,
- the acidity or basicity of the salt solution
- depends on the relative strengths of the acid and
base.
65Salts that Contain Acidic Cations and Basic
Anions
- If the acid cation is stronger than the base
anion, it wins and the salt solution is acidic.
- If the base anion is stronger than the acid
cation, it wins and the salt solution is basic.
66Salts that Contain Acidic Cations and Basic
Anions
- Ka gt Kb
- the acid cation is stronger and the salt
solution is acidic. - Ka lt Kb
- the base anion is stronger and the salt
solution is basic. - Ka ? Kb
- the salt solution is close to neutral.
67Problem
- Classify each of the following salts as acidic,
basic, or neutral - a) KBr
- b) NaNO2
- c) NH4Br
- d) NH4F
Ka for HF 6.6 x 10-4 Kb for NH3 1.8 x 10-5
68The Common-Ion Effect
- Solutions consisting of both an acid and its
conjugate base are very important because they
are very resistant to changes in pH. Such buffer
solutions regulate pH in a variety of biological
systems.
69The Common-Ion Effect
- Lets consider a solution made of 0.10 moles of
acetic acid and 0.10 moles of sodium acetate with
a total volume of 1.00 L, making the initial
CH3COOH CH3COO- 0.10 mol/L. - First we must identify all potential acids and
bases in the system. -
- CH3COOH CH3COO- Na
H2O - acid base
neutral acid -
or base
70Point of view of the acid
- Our reaction will be
- CH3COOH (aq) H2O (l) ? H3O (aq) CH3COO- (aq)
- Ka 1.8 x 10-5
Note that the initial concentration of our
product CH3COO- is NOT ZERO!
71- Lets check the
- initial acid concentration / Ka ratio.
- 0.10 / 1.8 x 10-5 ? 5500
- Its probably safe to assume that
- x ltlt HAci so HAceqm ? HAcI
- and x ltlt Ac-i so Ac-eqm ? Ac-i
- 1.8 x 10-5 x (0.10 x) / (0.10 x)
- 1.8 x 10-5 x (0.10) / (0.10)
- x 1.8 x 10-5 mol/L
72- At equilibrium,
- H3O 1.8 x 10-5 mol/L
- CH3COO- 0.10 1.8 x 10-5 0.10 mol/L
- CH3COOH 0.10 - 1.8 x 10-5 0.10 mol/L
- Assumption was valid! Check for yourself!
- pH - log H3O
- pH - log 1.8 x 10-5
- pH 4.74
73If we had started out with only 0.10 mol/L acetic
acid, the pH would be found from
74- The initial acid concentration / Ka will still be
the same, so we can assume - x ltlt HAci so HAceqm ? HAci
- 1.8 x 10-5 x2 / (0.10 x)
- 1.8 x 10-5 x2/ (0.10)
- x ?1.8 x 10-6 mol/L
- x ?1.3 x 10-3 mol/L (cant be ve)
- pH - log H3O
- pH - log 1.3 x 10-3
- pH 2.89
75- Without the acetate ion the pH of
- 0.10 M acetic acid is 2.89.
- With an equal concentration of acetate ion
present, the pH of - 0.10 M acetic acid 0.10 M acetate is 4.74
- The acetate ion makes a large difference on the
equilibrium pH!
76CH3COOH (aq) H2O (l) ? H3O (aq) CH3COO- (aq)
- Adding the conjugate base (a stress!) to the
equilibrium system of an acid dissociation shows
the common-ion effect, where the addition of a
common ion causes the equilibrium to shift. - This is an example of Le Chataliers Principle.
Addition of the weak base to the acid dissociation
77Problem
- Calculate the concentrations of all species
present, and the pH in a solution that is 0.025
mol/L HCN and 0.010 mol/L NaCN. - (Ka of HCN 4.9 x 10-10)
78Problem
The initial base concentration / Ka ratio is
0.010 / 4.9 x 10-10 ? 2 x 107 Its probably safe
to assume that x ltlt HCNi so HCNeqm ?
HCNI and x ltlt CN-i so CN-eqm ? CN-i
79Problem
4.9 x 10-10 x (0.010 x) / (0.025 x) 4.9 x
10-10 x (0.010) / (0.025) x 1.2 x 10-9
mol/L So at equilibrium, H3O 1.2 x 10-9
mol/L CN- 0.010 1.2 x 10-9 0.010 mol/L
HCN 0.025 - 1.2 x 10-9 0.025
mol/L. Assumption was valid! Check this for
yourself!
80Problem
pH - log H3O pH - log 1.2 x 10-9 pH 8.91
81Buffer Solutions
- Solutions that contain both a weak acid and its
conjugate base are buffer solutions. - These solutions are resistant to changes in pH.
82Buffer Solutions
- If more acid (H3O) or base (OH-) is added to the
system, the system has enough of the original
acid and conjugate base molecules in the solution
to react with the - added acid or base, and so the new equilibrium
mixture will be - very close in composition to the original
equilibrium mixture.
83Buffer solutions
- A 0.10 mol?L-1 acetic acid 0.10 mol?L-1 acetate
mixture has a pH of 4.74 and is a buffer
solution! - CH3COOH (aq) H2O (l) ? H3O (aq) CH3COO- (aq)
84Buffer solutions
- If we rearrange the Ka expression to solve for
- H3O
85Buffer solutions
- Assume x ltlt HAci so HAceqm ? HAcI
- and x ltlt Ac-i so Ac-eqm ? Ac-i,
- and we should see
- If CH3COOHi CH3COO-i,
- then H3O 1.8 x 10-5 M Ka
- and pH pKa 4.74
86Buffer solutions
- What happens if we add 0.01 mol of NaOH (strong
base) to 1.00 L of the acetic acid acetate
buffer solution? - CH3COOH (aq) OH- (aq) ? H2O (l) CH3COO- (aq)
- This reaction goes to completion and keeps
occurring until we run out of the limiting
reagent OH-
New CH3COOH 0.09 M and new CH3COO- 0.11 M
87Buffer solutions
- With the assumption that x is much smaller than
0.09 mol (an assumption we always need to check
after calculations are done!), we find
Note weve made the assumption that x ltlt 0.09
M! pH - log H3O pH - log 1.5 x 10-5 pH
4.82
88Buffer solutions
- Adding 0.01 mol of OH- to 1.00 L of water would
have given us a pH of 12.0 because there is no
significant amount of acid in water for the base
to react with. - Our buffer solution resisted this change in pH
because there is a significant amount of acid
(acetic acid) for the added base to react with.
89Buffer solutions
- What happens if we add 0.01 mol of HCl (strong
acid) to 1.00 L of the acetic acid acetate
buffer solution? - CH3COO- (aq) H3O (aq) ? H2O (l) CH3COOH (aq)
- This reaction goes to completion and keeps
occurring until we run out of the limiting
reagent H3O
New CH3COOH 0.11 M and new CH3COO- 0.09 M
90Buffer solutions
- With the assumption that x is much smaller than
0.09 mol (an assumption we always need to check
after calculations are done!), we find
Note weve made the assumption that x ltlt 0.09
M! pH - log H3O pH - log 2.2 x 10-5 pH
4.66
91Buffer solutions
- Adding 0.01 mol of H3O to 1.00 L of water would
have given us a pH of 2.0 because there is no
significant amount of acid in water for the base
to react with. - Our buffer solution resisted this change in pH
because there is a significant amount of base
(acetate) for the added acid to react with.
92.
93Buffer capacity
- Buffer capacity is the measure of the ability of
a buffer to absorb acid or base without
significant change in pH. - Larger volumes of buffer solutions have a larger
buffer capacity than smaller volumes with the
same concentration. - Buffer solutions of higher concentrations have a
larger buffer capacity than a buffer solution of
the same volume with smaller concentrations.
94Problem
- Calculate the pH of a 0.100 L buffer solution
that is 0.25 mol/L in HF and 0.50 mol/L in NaF.
With the assumption that x is much smaller than
0.25 mol (an assumption we always need to check
after calculations are done!), we find
Assume x ltlt HCNi so HCNeqm ? HCNi and x ltlt
CN-i so CN-eqm ? CN-i
95Problem
pH - log H3O pH - log 1.75 x 10-4 pH 3.76
96Problem
- a) What is the change in pH on addition of 0.002
mol of HNO3?
New HF 0.27 M and new F- 0.48 M
97Problem
Notice weve made the assumption that x ltlt 0.27
M. We should check this! pH - log H3O pH
- log 1.97 x 10-4 pH 3.71
98Problem
- b) What is the change in pH on addition of 0.004
mol of KOH?
New HF 0.21 M and new F- 0.54 M
99Problem
Notice weve made the assumption that x ltlt 0.21
M. We should check this! pH - log H3O pH
- log 1.36 x 10-4 pH 3.87
100The Henderson-Hasselbalch Equation
- Weve seen that, for buffer solutions containing
members of a conjugate acid-base pair, that - pH pKa log base / acid
- This is called the Henderson-Hasselbalch
Equation.
101The Henderson-Hasselbalch Equation
- If we have a buffer solution of a conjugate
acid-base pair, then the pH of the solution will
be close to the pKa of the acid. - This pKa value is modified by the logarithm of
ratio of the concentrations of the base and acid
in the solution to give the actual pH.
102Problem
- Use the Henderson-Hasselbalch Equation to
calculate the pH of a buffer solution prepared by
mixing equal volumes of 0.20 mol/L NaHCO3 and
0.10 mol/L Na2CO3. - We need the Ka and the concentrations of the acid
(HCO3-) and the base (CO32-). - Ka 5.6 x 10-11
- (we use the Ka for the second proton of H2CO3!).
103Problem
- NOTE The concentrations we are given for the
acid and the base are the concentrations - before the mixing of equal volumes!
104Problem
- If we mix equal volumes, the total volume is
TWICE the volume for the original acid or base
solutions. - Since the number of moles of acid or base DONT
CHANGE on mixing, - the initial concentrations we use will be
- half the given values.
- pH pKa log base / acid
- pH (-log 5.6 x 10-11) log (0.05) / (0.10)
- pH 10.25 0.30
- pH 9.95