Title: Chapter 16  Acid-Base Equilibria
 1Chapter 16 Acid-Base Equilibria
- Dr. Peter Warburton 
- peterw_at_mun.ca 
- http//www.chem.mun.ca/zcourses/1011.php
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 1.3 x 10-4 pH  3.89 
 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(No Transcript) 
 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 HFi so HFeqm ? HFi and x ltlt 
F-i so F-eqm ? F-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