Chemistry 12 Notes on Unit 4

Practical Aspects of Titration

Remember, standard solutions are solutions of accurately known

concentration. They are put into a burette and used to titrate solutions of
Burette unknown concentration (sample solutions)

Can solid NaOH be used to prepare a Standard Solution (by weighing it

and dissolving it in a known volume of water)? _________( See sample)

Answer: NaOH cannot be weighed accurately as it absorbs water and CO2

Standard from the air as it’s being weighed. (it’s hygroscopic)
Solution
There are 2 ways to prepare a standard solution accurately:

1. Use a Primary Standard

A Primary Standard has the following characteristics:

It is obtained in pure and stable form & dissolves completely

It does NOT absorb H2O or CO2 from the air. (non-hygroscopic)
It has an accurately known molar mass
Sample It reacts quickly and completely with the sample
Solution
An accurately measured mass of the primary standard is weighed and
dissolved in an accurately measured volume of water to obtain a solution
of accurately known concentration. (Standard Solution)

Eg.) 40.48 g of potassium hydrogen phthalate (KHC8H4O4) is weighed out and dissolved in enough distilled water
to make 1.000 L of solution. Find the [KHC8H4O4]. (HINT: Use g moles M )

Some Primary Standards are:

• Na2CO3 (sodium carbonate)
• KHC8H4O4 (potassium hydrogen phthalate)
• C6H5COOH (benzoic acid)

NEVER NaOH remember, it is highly hygroscopic!

2. Standardizing a Solution
This is done by titrating a solution with a primary standard in order to find it’s accurate concentration .
The standardized solution can then be used to titrated other solutions.
titrates titrates
Eg.) A Primary Standard Acid A base solution (eg. NaOH) Other acids of unknown conc.

Example:
It takes 4.02 mL of 0.200 M KHC8H4O4 to titrate 10.00 mL of a solution of NaOH. Find the [NaOH]

The balanced equation for the reaction is : KHC8H4O4 + NaOH H2O + KNaC8H4O4

So the [NaOH] = _____________ M

Chemistry 12—Notes on Unit 4 Page 54

Chemistry 12 Notes on Unit 4

This standardized NaOH solution can now be used to titrate other acids of unknown concentration:

Eg.) It takes 28.54 mL of standardized 0.0804 M NaOH to titrate a 25.00 mL sample of an H2SO4 solution.

The balanced equation for this neutralization reaction is:

Calculate the [H2SO4].

Answer [H2SO4] = ___________ M

Carefully read p. 164 – 165 in SW.

Do Ex. 121 – 123 on p. 165

Finding the pH of Mixtures of Acids and Bases

Type 1 – When the mole ratio (coefficient ratio) is 1:1

NOTE: In acid base reactions, if one or both of the reactants are “strong” then the reaction will go to completion.
Only when both reactants are “weak”, will you get an equilibrium situation. Titrations always require reactions
which go to completion (single arrow), so acid/base titrations will always have either a strong acid, a strong base,
or both.
Recall excess or “left over reactant” problems from Chem. 11? Read the following eg. & make sure you
understand.

Eg.) If 3 moles of NaOH are mixed with 1 mole of HCl, what will happen?
3 mol 1mol
NaOH + HCl H2O + NaCl
What will happen here is: 1 mol of HCl will react with 1 mole of NaOH (1:1 coefficient ratio) to form 1 mol of
H2O and 1 mol of NaCl. 3 – 1 = 2 mol of NaOH will be left over. The NaOH is said to be IN EXCESS by 2 mol.
The resulting solution, consisting of H2O (neutral), NaCl (neutral) and left over NaOH (basic), will be basic. (All
the HCl (limiting reactant) has been used up, so there is none of that left.)

Example Question:
10.00 mL of 0.100M NaOH is mixed with 25.00 mL of 0.100 M HCl. Find the pH of the final (resulting) mixture.

Solution: Balanced equation: NaOH + HCl H2O + NaCl

Initial moles of NaOH : 0.100 M x 0.01000 L = 0.00100 mol NaOH (3 SD’s like the 0.100 M) (5 dec. places)

Initial moles HCl : 0.100 M x 0.02500 L = 0. 00250 mol HCl (3 SD’s like the 0.100 M) (5 dec. places)

Excess moles: HCl = 0.00150 mol HCl (5 dec. places) (3 SD’s)

Volume of final mixture: 10.00 mL + 25.00 mL = 35.00 mL = 0.03500 L

(2 dec. pl.) (2 dec. pl.) (2 dec. pl.) (4 SD’s)
(4 SD’s) 3 SD’s but DON’T round
here. Leave it in your
calculator, unrounded! For
[H3O+] = [HCl] in the final mixture = 0.00150 mol (3 SD’s) = 0.042857 M the next step
0.03500 L (4 SD’s)

Chemistry 12—Notes on Unit 4 Page 55

Chemistry 12 Notes on Unit 4

pH = - log [H3O+] = - log (0.042857) = 1.368 (rounded to 3 SD’s)

Remember, when adding or subtracting, use decimal places, when multiplying or dividing, use SD’s.

When the base is in excess (eg. Excess NaOH):

Moles NaOH in excess ( [NaOH] = [OH-] ) pOH pH

Try the following example. (Pay close attention to significant digits and decimal places, but don’t round in
your calculator until the last step.)

40.00 mL of 0.100 M NaOH is mixed with 25.00 mL of 0.100 M HCl. Calculate the pH of the solution
resulting. Show all of your steps. Express your answer in the correct # of SD’s as justified by the data.

Type 2 – When the mole ratio (coefficient ratio) is NOT 1:1

• Think of a diprotic acid as releasing 2 protons (H+’s) to the base.

(NOTE: even though we learned that diprotic acids like H2SO4, donate only 1 proton completely, that was to
WATER, not to a STRONG BASE. A STRONG BASE will take both the protons from H2SO4!)

• Dissociate bases to find out the number of OH- ions they provide.

• Calculate excess moles of H+ or OH- rather than moles of acid or base as you did in type 1.

Eg.) 15.00 mL of 0.100 M H2SO4 is mixed with 12.50 mL of 0.200 M NaOH. Calculate the pH of the resulting
solution.
Solution to Problem:
Balanced equation for the reaction: H2SO4 + 2NaOH 2 H2O + Na2SO4 (NOT a 1:1 reactant mole ratio!)

Dissociations: H2SO4 2 H+ + SO42- NaOH Na+ + OH-

Initial moles of H+: 0.100 M x 0.01500 L = 0.00150 mol H2SO4 x 2 mol H+ = 0.00300 mol H+ (3SD’s 5 dps)
1 mol H2SO4

Initial moles OH- : 0.200 M x 0.01250 L = 0. 00250 mol NaOH x 1 mol OH- = 0.00250 mol OH-(3SD’s 5 dps)
1 mol NaOH

Excess moles H+ = 0.00050 mol (5dp 2SD’s)

Volume of final mixture: 15.00 mL + 12.50 mL = 27.50 mL = 0.02750 L

(2 dec. pl.) (2 dec. pl.) (2 dec. pl.) (4 SD’s)
(4 SD’s)

[H3O+] = [H+] in the final mixture = 0.00050 mol (2 SD’s) = 0.0181818 M

0.02750 L (4 SD’s)

pH = - log [H3O+] = - log (0.0181818) = 1.74 (rounded 2 SD’s)

Chemistry 12—Notes on Unit 4 Page 56

Chemistry 12 Notes on Unit 4

Do Ex. 58, 59 and 60 on p. 143 of SW.

Titration Curves
Burette

Base of Known
Conc.

pH Beginning of a
titration curve

pH probe

Acid of Volume of Base

known conc.

A base of known concentration is slowly added to a measured volume of an acid of known concentration.
Meanwhile, the pH of the mixture is monitored by a pH probe attached to a computer. The computer plots a graph
of pH vs. Volume of Base Added. The curve on the graph that results from this is called a titration curve.

You will be doing this as a lab. However, you will also be expected to be able to calculate the pH’s needed to
plot a titration curve for a Strong Acid—Strong Base titration.

Strong Acid—Strong Base (SA/SB) Titration Curves

We can calculate the pH of the mixture in the beaker throughout the titration. First, we separate the process
into 4 stages:

1. Acid before any base is added

2. Base added but acid in excess
3. Equivalence (Stoichiometric) Point
4. Base in excess

Stage 1—Acid before any base is added

The beaker contains 25.00 mL of 0.100 M HCl. Calculate the pH.

HCl is a SA, so [H3O+] = [acid] = 0.100 M

and pH = -log (0.100) = 1.000

Chemistry 12—Notes on Unit 4 Page 57

Chemistry 12 Notes on Unit 4

Stage 2—Base added but acid in excess

5.00 mL of 0.100 M NaOH is added to 25.00 mL of 0.100 M HCl. Find the pH of the resulting solution.

Solution: Balanced equation: NaOH + HCl H2O + NaCl

Initial moles of NaOH : 0.100 M x 0.00500 L = 0.000500 mol NaOH (3 SD’s like the 0.100 M) (6 dec. places)

Initial moles HCl : 0.100 M x 0.02500 L = 0. 00250 mol HCl (2 SD’s like the 0.100 M) (5 dec. places)

Excess moles: HCl = 0.00200 mol HCl (5 dec. places) (3 SD’s)

Volume of final mixture: 5.00 mL + 25.00 mL = 30.00 mL = 0.03000 L

(2 dec. pl.) (2 dec. pl.) (2 dec. pl.) (4 SD’s)
(4 SD’s) 3 SD’s but DON’T
round here. Leave it in
your calculator,
[H3O+] = [HCl] in the final mixture = 0.00200 mol (3 SD’s) = 0.06667 M unrounded, for the next
0.03000 L (4 SD’s) step.

pH = - log [H3O+] = - log (0.06667) = 1.176 (rounded to 3 SD’s)

Stage 3—Equivalence (Stoichiometric) Point
25.00 mL of 0.100 M NaOH is added to 25.00 mL of 0.100 M HCl. Find the pH of the resulting solution.

Solution: Balanced equation: NaOH + HCl H2O + NaCl

Initial moles of NaOH : 0.100 M x 0.02500 L = 0.00250 mol NaOH (3 SD’s like the 0.100 M) (5 dec. places)

Initial moles HCl : 0.100 M x 0.02500 L = 0. 00250 mol HCl (2 SD’s like the 0.100 M) (5 dec. places)

Excess moles: Neither HCl nor NaOH is in excess

However, 0.00250 moles of H2O and 0.00250 moles of NaCl have been produced:

NaOH + HCl H 2O + NaCl

Initial moles 0.00250 0.00250 0 0
Change in moles -0.00250 -0.00250 + 0.00250 + 0.00250
Final moles 0 0 0.00250 0.00250
The NaOH and the HCl have completely neutralized each other. There is no SA or SB left!
The two substances which remain are H2O which is neutral and won’t affect pH.
And the salt NaCl(aq) Na+(aq) + Cl- (aq)

The cation from a SB The anion from a SA

(eg. any alkali ion) is (top 5 on right) is
always NEUTRAL! always NEUTRAL!

THE SALT FORMED FROM A SA-SB TITRATION IS ALWAYS NEUTRAL

Since there is no SA, no SB and just H2O and a NEUTRAL salt, the pH of the solution formed will be 7.00

At the Equivalence (Stoichiometric)Point of a SA—SB Titration, the pH is always = 7.00

Chemistry 12—Notes on Unit 4 Page 58

Chemistry 12 Notes on Unit 4

Stage 4—Base in Excess

26.00 mL of 0.100 M NaOH is added to 25.00 mL of 0.100 M HCl. Find the pH of the resulting solution.

Solution: Balanced equation: NaOH + HCl H2O + NaCl

Initial moles of NaOH : 0.100 M x 0.02600 L = 0.00260 mol NaOH (3 SD’s like the 0.100 M) (5 dec. places)

Initial moles HCl : 0.100 M x 0.02500 L = 0. 00250 mol HCl (2 SD’s like the 0.100 M) (5 dec. places)

Excess moles: NaOH = 0.00010 mol NaOH (5 dec. places) (2 SD’s)

Volume of final mixture: 26.00 mL + 25.00 mL = 51.00 mL = 0.05100 L

(2 dec. pl.) (2 dec. pl.) (2 dec. pl.) (4 SD’s)
(4 SD’s) 2 SD’s but DON’T round
here. Leave it in your
calculator, unrounded! For
[OH-] = [NaOH] in the final mixture = 0.00010 mol (2 SD’s) = 0.00196 M the next step
0.05100 L (4 SD’s)

pOH = - log [OH-] = - log (0.00196) = 2.70757 (leave unrounded in calculator)

pH = 14.000 – pOH = 11.29 Now, round to

2 SD’s

Notice how adding just 1.00 mL extra 0.100 M NaOH, made the pH shoot up from 7.00 to 11.29 (a jump of
over 4 pH units!)

Plotting a SA—SB Titration Curves

Using the processes outlined in “Stage 1 to Stage 4” above, calculate the pH of the resulting solutions formed by
adding the given volumes of 0.10 M NaOH to 25.00 mL of 0.10 M HCl. Work out your answers on a separate sheet
(or on your calculator) and record them in the following table:

Volume of 0.10 M NaOH (mL) Volume of 0.10 M HCl (mL) pH of Resulting Solution
0.00 25.00 No base added
5.00 25.00 1.18
15.00 25.00
20.00 25.00 Base added
24.00 25.00 Acid in excess

24.50 25.00
24.90 25.00
25.00 25.00 Equivalence Pt.
25.10 25.00
25.50 25.00
26.00 25.00 11.29 Base in excess

30.00 25.00
40.00 25.00
50.00 25.00

Check with the teacher to make sure your pH values are correct! Then go on to the next step:

Chemistry 12—Notes on Unit 4 Page 59

Chemistry 12 Notes on Unit 4

Now, go to a computer and make a graph with Volume of NaOH on the “X” axis and pH on the “Y” axis. You can
use Microsoft Excel and follow the instructions below:

1. Log on
2. Go to “Start” then “Programs” and select “Microsoft Excel”.
3. Enter the values for “Volume of 0.10M NaOH” from the table in Column “A” (No words!)
4. Enter the values for pH (to 2 decimal places) in column “B” (No words!)
5. When finished entering numbers, click in the cell “C 1”
6. Now click the “Chart Wizard”
icon near the top of the screen.
7. Select “XY (Scatter)”
8. When the “Chart
Sub-Types” box
comes up, click on
the MIDDLE LEFT
box
9. Click the “Next” button at the
bottom of the screen.

10. When the next thing comes up, click the “Next” button again. Click “Titles” if it isn’t already selected.
11. In the “Chart Title:” enter “Strong Acid-Strong Base Titration Curve followed by your names”
12. In the “Value (X) axis:” box, enter “Volume of NaOH”
13. In the “Value (Y) axis:” box, enter “pH”
14. Click the “Legend” tab at the top, then click in the box that says “Show Legend” to remove the
checkmark
15. Now, click the “Next” button at the bottom
16. IMPORTANT: Click the little round button next to “As New Sheet”
17. Now click “Finish”
18. Save and Print enough copies of the graph for the people in your group.
19. Keep it. Your teacher will have you add some important information to it.

Do Experiment 20-H—Using the pH Probe and Computer to do a Strong Acid—Strong Base

Titration. See the internet site: http://wwwchem.uwimona.edu.jm:1104/software/titr.html !

Weak Acid—Strong Base Titration Curves

Again, this type of titration has the 4 stages:

1. Acid before any base is added

2. Base added but acid in excess
3. Equivalence (Stoichiometric) Point
4. Base in excess

When the acid in the beaker is WEAK, stages 1-3 are different than in a SA-SB titration.

Stage 1 – Only the Acid is present, but it is a WEAK acid, so the [H3O+] is NOT equal to [acid]
To find [H3O+] and pH, you have to use an ICE table.

Chemistry 12—Notes on Unit 4 Page 60

Chemistry 12 Notes on Unit 4

Eg. Find the pH of 25.00 mL of 0.10 M CH3COOH before any base is added to it.

Solution:
CH3COOH + H2O H3O+ + CH3COO-
[I] 0.10 0 0
[C] -x +x +x
[E] 0.10 –x x x

1. Ka expression: Ka = [H3O+][CH3COO-]
[CH3COOH]
Ka = (x) (x)
0.10 - x Assume 0.10 – x ≅ 0.10
Ka ≅ x2
0.10

So x2 = 0.10 Ka

[H3O+] = x = 0.10 Ka

= 0.10 (1.8 x 10-5)

[H3O+] = 1.34164 x 10-3 M

pH = 2.87
We see that for a WEAK Acid-Strong Base Titration, the pH before the base is added is higher (eg. 2.87)
than it was for a SA-SB Titration (where the pH before the base is added was 1.00)
For the same concentration, the weaker the acid, the HIGHER the pH will start out!

Stage 2—Base Present with Acid in Excess

Eg. 10.00 mL of 0.100 M NaOH is added to 25.00 mL of 0.10 M CH3COOH.

Solution: Balanced equation: NaOH + CH3COOH H2O + NaCH3COO

Initial moles of NaOH : 0.100 M x 0.01000 L = 0.00100 mol NaOH

Initial moles CH3COOH : 0.100 M x 0.02500 L = 0. 00250 mol CH3COOH

Excess moles: CH3COOH = 0.00150 mol CH3COOH

But, this time we must consider the salt (NaCH3COO) that is produced because it is NOT neutral!

NaOH + CH3COOH H 2O + NaCH3COO

Initial moles 0.00100 0.00250 0 0
Change in moles -0.00100 -0.00100 + 0.00100 + 0.00100
Final moles 0 0.00150 0.00100 0.00100

A Weak The salt of it’s

Acid Conjugate Base

Chemistry 12—Notes on Unit 4 Page 61

Chemistry 12 Notes on Unit 4

What we are left with is a mixture of a Weak Acid (CH3COOH) and the Salt of It’s Conjugate Base (NaCH3COO)

A mixture of a Weak Acid and a Weak Base (the Salt of It’s Conjugate Base) is called a BUFFER SOLUTION.

As we will see later, a Buffer Solution is a solution which maintains the pH at a fairly Constant value.
This causes the Titration Curve to decrease in slope during this stage. The area on the curve is called the
“Buffer Region”.

(In Chem. 12, we will not need to be able to calculate the pH in a Buffer Solution.)

Stage 3—Equivalence (Stoichiometric) Point

Eg. 25.00 mL of 0.100 M NaOH is added to 25.00 mL of 0.10 M CH3COOH.

Solution: Balanced equation: NaOH + CH3COOH H2O + NaCH3COO

Initial moles of NaOH : 0.100 M x 0.02500 L = 0.00250 mol NaOH

Initial moles CH3COOH : 0.100 M x 0.02500 L = 0. 00250 mol CH3COOH

Excess moles: neither NaOH nor CH3COOH is in excess

But, this time we must consider the salt (NaCH3COO) that is produced because it is NOT neutral!

NaOH + CH3COOH H 2O + NaCH3COO

Initial moles 0.002500 0.00250 0 0
Change in moles -0.00250 -0.00250 + 0.00250 + 0.00250
We have produced 0.00250
Final moles 0 0 0.00250 0.00250 moles of the salt NaCH3COO
(CH3COO-)
Negligible compared to
water already present

This salt that is produced (NaCH3COO) dissociates to form Na+ (spectator) and CH3COO- which undergoes
base hydrolysis in water.
The total volume of our solution is 25.00 + 25.00 = 50.00 mL = 0.05000 L.

So the [CH3COO-] = 0.00250 mol = 0.0500 M

0.05000 L

The Kb for CH3COO- = 1.0 x 10-14 / 1.8 x 10-5 = 5.556 x 10-10

We can now use the hydrolysis equation and an ICE table to calculate the [OH-] and then pOH and then pH:

. CH3COO- + H2O CH3COOH + OH-

[I] 0.0500 0 0
[C] -x +x +x
[E] 0.0500 –x x x

Kb expression: Kb = [CH3COOH] [ OH-]

[CH3COO-]

Kb = x2
0.0500 - x Assume 0.0500 – x ≅ 0.0500

Chemistry 12—Notes on Unit 4 Page 62

Chemistry 12 Notes on Unit 4

Kb ≅ x2
0.0500

So x2 = 0.0500 Kb

[OH-] = x = 0.0500 Kb

[OH-] = 0.0500 (5.556 x 10-10) = 5.270 x 10-6 M pOH = 5.278 pH = 8.72

For a WA/SB Titration, the pH at Equivalence Point is ALWAYS > 7

This is because, when a Weak Acid reacts with a Strong Base, you always produce the conjugate base of the weak
acid, which is BASIC.

Remember: For a SA/SB Titration, the salt produced has the conjugate base of a STRONG ACID, which is always
Neutral so for a SA/SB Titration, the pH at EP (SP) is ALWAYS = 7.00
Stage 4 – Base in excess:

Looking at the Balanced equation: NaOH + CH3COOH H2O + NaCH3COO

Once NaOH is in Excess, you will have some STRONG BASE (NaOH) and some WEAK BASE (CH3COO-) in the
resulting mixture. The OH- contributed by the weak base ( CH3COO-)was significant when there was no other base
present (EP), but once a strong base (NaOH) is present, the OH- contributed by the weak base is insignificant
compared to that produced by the NaOH. So the titration curve past the EP for a WA/SB Titration is the same as it is
for a SA/SB Titration (where NaOH is in excess)

See the next page for a graph for the titration of CH3COOH with NaOH (A Weak Acid/Strong Base Titration):

Chemistry 12—Notes on Unit 4 Page 63

Chemistry 12 Notes on Unit 4

Weak Acid - Strong Base Titration Curve

14

Shorter almost
12 vertical region than
in SA/SB

10

Buffer pH at Equivalence
8 Region Point is > 7
pH

0
0 10 20 30 40 50 60
Volume of NaOH

pH starts higher Drop in slope

than SA/SB when buffer
kicks in

See the next page for a Strong Acid-Weak Base Titration Curve…

Chemistry 12—Notes on Unit 4 Page 64

Chemistry 12 Notes on Unit 4

Strong Acid—Weak Base Titration Curves

In this type of titration, the Standard Solution is usually the Strong Acid and the Sample is usually the Weak Base.
Therefore, the SA will be in the burette and the WB will be in the beaker:
An example of a SA/WB Titration could
Burette be done with the strong acid HCl and the
weak base NH3.

HCl + NH3 NH4+ + Cl-

SA (HCl)
The pH will start out high (base), but not
too high (weak)

When HCl is added but the NH3 is still in

excess, we will have a mixture of NH3 (a
weak base) and NH4+ (a weak acid) which
is a buffer. So again, we will have a buffer
region as the pH goes down.
pH probe
At the equivalence point in this titration,
all of the HCl and NH3 will be gone and
Weak Base only NH4+ (a weak acid) and Cl- (a
(NH3) neutral spectator) will remain. Because
there is a WEAK ACID (NH4+) present,
the pH will be LESS THAN 7. (but not
really low)

Once the Acid (HCl) is in excess, the pH will continue to go down.

Read the information above and see if you can make an informed guess at what the Titration Curve for this SA/WB
Titration would look like. Label the Equivalence Point. When you are finished, check with the teacher!

pH

Volume of HCl

Chemistry 12—Notes on Unit 4 Page 65

Chemistry 12 Notes on Unit 4

Summary of pH at Equivalence (Stoichiometric) Points for the three types of Titrations:

Reactants Salt Formed is… pH at Equivalence Point

Strong Acid – Strong Base Neutral (conjugate base of SA) = 7.00
Weak Acid – Strong Base Basic (conjugate base of WA) > 7.00
Strong Acid – Weak Base Acidic (conjugate acid of WB) < 7.00

Make sure you study and KNOW this table. It is very important!

Indicators for Titrations

Indicators can be used to tell you when you have reached the Equivalence (Stoichiometric) Point in a Titration.

However, different indicators must be used for different types of titrations.

Ideally, the pH at the Transition Point (pKa) of the Indicator will be the same as the pH at the Equivalence Point of
the titration. Or:

pKa (indicator) = pH at EP of Titration

To choose the best indicator for a particular titration, have the titration curve and the indicator table handy:

For example, for a SA-SB Titration Curve:

14

12

10

8 Any indicator with pKa

pH
pH = 7
in this range would be
6
at EP
suitable.

0
10 20 30 40 50
volume (cm³)
The best indicators are the ones which have the pH at EP within their Transition Range. So the best indicators for
the SA-SB Titration above would be Bromthymol Blue (Range 6.0 – 7.6) , Phenol Red (Range 6.6 – 8.0) or Neutral
Red (Range 6.8 – 8.0) as these all have pH =7 within their transition ranges.
However, looking at the graph, there is an almost vertical line from pH 3 to pH 11 on the graph. This means that
VERY LITTLE volume change of base would give a huge change in pH. It probably takes only a few drops to get
the pH to change from 3.0 to 11.0! Any of the indicators Bromcresol Green to Thymolphthalein would change
colour in that pH range, so they would all work for this one.

Next, we will look at a WA – SB Titration:

See the next page….

Chemistry 12—Notes on Unit 4 Page 66

Chemistry 12 Notes on Unit 4

For a WA-SB Titration Curve:

14

12

10
pH at EP
8
=9
pH
6

0
10 20 30 40 50

For a WA-SB Titration Curve, the almost vertical section is shorter (than for the SA-SB Curve). This means you
have a narrower range of suitable indicators. For this particular titration, any indicator which has pH = 9 within it’s
Transition Range is suitable.
Indicators Suitable for this WA – SB Titration would include ______________________________________,

__________________________________________ or ___________________________________________
Now for a SA – WB Titration Curve:
14

12

10

8
pH
6
pH at EP
5
4

0
10 20 30 40 50

Indicators Suitable for this SA – WB Titration would include

_________________________________________ or __________________________________________

Chemistry 12—Notes on Unit 4 Page 67

Chemistry 12 Notes on Unit 4

Question: Draw the titration curve you would expect would result from the following titration. Get the shape and the
important points (pH at beginning, pH at EP, pH at the end etc. ) as close as you can:

Burette

pH

0.10 M HNO3

25.0 mL of
0.10 M NaOH

Volume of HNO3
Name an indicator which would be suitable for this titration. ________________________________________

As you pass through the Equivalence (Stoichiometric) point in this titration, the colour of your indicator would
change from ____________________ to _______________________ (to ______________________ )

Using Titration Curves in Questions and Calculations

If we have a strong base (eg. NaOH or KOH) in the burette (“Volume of base” is on “X” axis), we can tell by the
shape and by the pH at the beginning (Volume of Base = 0) whether the acid is Strong or Weak (given the [acid])

For example, if we have a 0.10 M acid in the beaker and 0.10 M KOH in the burette and the titration curve looks
like:
14 Then we know that our acid must be a STRONG Acid because
the pH with no base added (Volume of base = 0 ) is 1.0. This means
12
[H3O+] = antilog (-pH) = antilog (-1.0) = 0.1 M. So, since
10 [H3O+] = [acid] we can see that this is a Strong Acid.
8
pH
Also the pH at EP = 7, which also signifies that we have a strong
6 acid.
4

2 At “Vol. Of KOH = 0”,

pH = 1
0
10 20 30 40 50
Volume of KOH
volume (cm³)

Chemistry 12—Notes on Unit 4 Page 68

Chemistry 12 Notes on Unit 4

By using the pH at “Volume of Base = 0”, we can calculate the Ka for a Weak Acid we are titrating.
Look at the following example in which a 0.10 M Weak Acid is 14
being titrated with 0.10 M NaOH.
12
Notice that the pH at “Volume of Base = 0” is about 2.5
10
Since pH = 2.5, [H3O+] = antilog (-2.5)
= 3.16 x 10-3 M 8
pH
6
Using [H3O+] = CoKa
4
We can rearrange and solve for Ka:
2
(squaring both sides:) [H3O+]2 = CoKa
0
10 20 30 40 50
so Ka = [H3O+]2 = (3.16 x 10-3 )2 = 1 x 10 –4 Volume of 0.10 M NaOH (mL)
Co 0.10

We can also use a titration curve to find the Volume of Base when the Equivalence point is reached. By knowing the
[acid], we use this “Volume of Base” to calculate the concentration of the Base. Look at the following example:

When titrating a 25.0 mL sample of 0.10 M HCl with a solution of NaOH, the following titration curve was
obtained. Calculate the [NaOH] in the burette:
14
We know that this is a SA-SB titration, so at the EP, pH = 7.
12 Also, the EP is always in the center of the “almost vertical”
region. We mark the EP and draw a straight line down to see
10 where is hits the “Volume of Base” axis. This will give us the
Volume of NaOH needed to reach the equivalence point:
8
14
pH
6
12

4
10

2
8
pH
0
10 20 30 40 50 6
Volume of NaOH (mL)
4
We see that the Volume of NaOH needed to reach the
Equivalence Point is approximately 32 mL. 2

0
Given this and the information at the beginning of the 10 20 30 40 50
question, calculate the [NaOH] in the burette: Volume of NaOH (mL)

Calculation:

[NaOH] = _________ M

Chemistry 12—Notes on Unit 4 Page 69

Chemistry 12 Notes on Unit 4

Question:

The following titration curve results from titrating 25.0 mL of a 0.10 M Weak Acid HA with a Strong Base KOH:
14
a.) Use this graph to estimate the Ka of the acid HA.
12

10

8
pH
6
b.) Use this graph to calculate the [KOH].
4

0
10 20 30 40 50
Volume of KOH (mL)

More Practical Things about Titrations

Selecting Solutions for Acid-Base Titrations

If you are titrating an acid, make sure you use a base so that your titration reaction is a neutralization. It should
have at least one STRONG reactant so it will go to completion.

For example, if you are titrating the acid CH3COOH (WA), use a STRONG BASE like NaOH, KOH etc. You could
not use another acid (like HCl etc.) . Also, since CH3COOH is a WEAK acid, you cannot use a weak base (like
NH3)

Also, the concentration of your standard should be relatively close to the concentration of the solution you are
titrating so that the volumes used are comparable. (So you don’t need “buckets” or “a fraction of a drop” )

Here is an example of a multiple choice question:

In titrating 25.00 mL samples of NH3 which is approximately 0.1 M, which of the following solutions should be
used to determine the [NH3]?
a) 0.00100M HCl b) 0.125 M HCl c) 6.00 M HCl d) 12.0 M HCl e) 0.100M NaOH

Too dilute. Right. HCl is Too Much too You can’t

You would a Strong concentrated. concentrated. titrate a WB
need too Acid and You would You would with a SB.
much volume conc. is close need too little need too little You need a
to 0.1 M volume volume SA.

Chemistry 12—Notes on Unit 4 Page 70

Chemistry 12 Notes on Unit 4

Buffer Solutions
A buffer solution is a solution which resists changes in pH when a small amount of acid or base is added.
Or we could say it minimizes the change in pH when acid or base is added.

Weak Acid Equilibria and the Common Ion Effect

Say you had some 1.0 M acetic acid (CH3COOH) solution.

This equilibrium becomes established:

. CH3COOH + H2O H 3O + + CH3COO-

[I] 1.0 0 0
[C] -x +x +x
[E]

A little less Low conc. Low conc.

than 1.0 M at at
at equilibrium equilibrium
equilibrium

Since CH3COOH is a WEAK acid, the [H3O+] and [CH3COO-] are quite low at equilibrium.

Now, lets add some sodium acetate (NaCH3COO) to the equilibrium mixture so that [ CH3COO-] is 1.0 M.

When we do this the [ CH3COO-] obviously goes up. However, by LeChatelier’s Principle, the equilibrium will
shift to the LEFT, causing [H3O+] to decrease and [CH3COOH] to increase

CH3COOH + H 2O H 3O + + CH3COO-

Concentration Concentration
Concentration
is a now a is a now a
is a now very
little > 1.0 M little < 1.0 M
low!

So what we have produced is a solution that has a fairly high ( 1M ) of a WEAK ACID (CH3COOH) and a
WEAK BASE (CH3COO- ) in the same solution. This is how a buffer solution is prepared.
Since the acid and the base are both WEAK, they don’t neutralize each other like a mixture of a SA and SB
would. They co-exist in this equilibrium unless disturbed!

There are two kinds of Buffer Solutions:

• A Weak Acid and the Salt of It’s Conjugate Base (WASCB) eg. 1.0 M CH3COOH & 1.0 M NaCH3COO
• A Weak Base and the Salt of It’s Conjugate Acid (WBSCA) eg. 1.0 M NH3 & 1.0 M NH4Cl

Chemistry 12—Notes on Unit 4 Page 71

Chemistry 12 Notes on Unit 4

The first type (WASCB) or Acidic Buffers are useful as buffers in the acidic range (solutions in which pH is 7 or lower)

The second type (WBSCA) or Basic Buffers are useful as buffers in the basic range (solutions in which pH is 7 or higher )

Any weak acid and a salt containing it’s conjugate base will work as an Acidic Buffer.
Any weak base and a salt containing it’s conjugate acid will work as a Basic Buffer.

Here are a few examples of buffer solutions:

Some Acidic Buffers (WASCB) Some Basic Buffers (WBSCA)

1.0 M HNO2 & 1.0 M KNO2 1.0 M NH3 & 1.0 M NH4Cl
0.1 M NaH2PO4 & 0.1 M Na2HPO4 1.0 M NH3 & 1.0 M NH4NO3
0.2 M H2C2O4 & 0.20 M NaHC2O4 1.0 M N2H4 & 1.0 M N2H5Br

NOTE: Buffers CANNOT be prepared using any STRONG ACIDS or STRONG BASES!!! Strong acids and
bases are too reactive, and will not remain in an equilibrium mixture. They will react!
So mixtures like 1.0 M HCl and 1.0 M NaCl or 1.0 M CH3COOH and 1.0 M NaOH CANNOT be Buffers!

Strong Strong
Acid Base

How Buffers Work to Minimize the Change in pH When Acids or Bases are Added

Consider the buffer solution made up of 1M CH3COOH and 1M NaCH3COO.

The equation representing the equilibrium present in this buffer solution is (just the same as the ionization of the weak
acid, CH3COOH):

CH3COOH + H 2O H 3O + + CH3COO-
1M low 1M

Now, we add a small amount of HCl to this solution.

The HCl produces H3O+, so the [H3O+] will immediately increase. (and the pH will go down).

However, since this is an equilibrium and there is plenty of CH3COO- available, the equilibrium will SHIFT to
the LEFT and [H3O+] will go back down again (but not quite to it’s original value)

This can be shown on a graph of [H3O+] vs. Time:

As equilibrium shifts left, [H3O+] decreases to

partially compensate for the sudden increase
[H3O+]
A very small net increase in
+
the [H3O ]

Time
HCl added

Chemistry 12—Notes on Unit 4 Page 72

Chemistry 12 Notes on Unit 4

Draw a graph of pH vs. Time when a small amount of HCl is added to the buffer above (Explain each part)

pH

Time
HCl added

Using the same buffer solution:

CH3COOH + H 2O H 3O + + CH3COO-
1M low 1M

This time we add a small amount of base NaOH:

The NaOH produces OH- which neutralizes H3O+ so the [H3O+] will immediately decrease. (and the pH will go up).

CH3COOH + H2O H3O+ + CH3COO-

However, since this is an equilibrium and there is plenty of CH3COOH available, the equilibrium will SHIFT to the
RIGHT and [H3O+] will go back up again (but not quite to it’s original value)
Equilibrium shifts to the RIGHT

CH3COOH + H 2O H 3O + + CH3COO-

This can be shown on a graph of [H3O+] vs. Time:

A very small net decrease

+
in the [H3O ]
[H3O+]

As equilibrium shifts right, [H3O+] increases to

partially compensate for the sudden decrease

Time
NaOH added

Draw a graph of pH vs. Time when a small amount of NaOH is added to the buffer above (Explain each part)

pH

Time
NaOH added

Chemistry 12—Notes on Unit 4 Page 73

Chemistry 12 Notes on Unit 4

So, in summary, this buffer maintains a relatively constant pH when a small amount of acid or base is added to it!

This is the function of a buffer solution!

Basic Buffers work using the same principles. Work through the example by filling in the blanks…..

Eg.) A buffer solution is prepared using 1M NH3 and 1M NH4Cl (WBSCA)

a) Write the equilibrium equation describing this buffer.

_________________________________________________________________________________

b) When a small amount of HCl (SA) is added, the [OH-] quickly _______creases (the pH goes ____ )

c) As a result, the equilibrium shifts to the _______________, and the [OH-] gradually _____creases. (the pH

goes back _________ )

d) So, as a result of adding HCl, there was a small net _____crease in the [OH-] (a small net ___ crease in pH )

e) Draw a graph of [OH-] vs. Time to illustrate what happened in b d. Label each part.

[OH-]

Time
HCl added

f) Draw a graph of pH vs. Time to illustrate what happened in b d.

pH

Time
HCl added

Chemistry 12—Notes on Unit 4 Page 74

Chemistry 12 Notes on Unit 4

Eg.) A buffer solution is prepared using 1M NH3 and 1M NH4Cl (WBSCA)

a) Write the equilibrium equation describing this buffer.

_________________________________________________________________________________

b) When a small amount of NaOH (SB) is added, the [OH-] quickly _______creases (the pH goes ____ )

c) As a result, the equilibrium shifts to the _______________, and the [OH-] gradually _____creases. (the pH

goes back _________ )

d) So, as a result of adding NaOH, there was a small net _____crease in the [OH-] (a small net ___ crease in pH )

e) Draw a graph of [OH-] vs. Time to illustrate what happened in b d. Label each part.

[OH-]

Time
NaOH added

f) Draw a graph of pH vs. Time to illustrate what happened in b d.

pH

Time
NaOH added

So, in summary, this buffer _______________________________________________________ when a small

amount of acid or base is added to it!

Chemistry 12—Notes on Unit 4 Page 75

Chemistry 12 Notes on Unit 4

Limitations of Buffers

Say we have a buffer solution prepared using 1M CH3COOH and 1M NaCH3COO. The equilibrium describing this
buffer solution is:

CH3COOH + H 2O H 3O + + CH3COO-
1M low 1M

Let’s say we add 1.5 moles of HCl to 1 Litre of this solution. The [H3O+] will immediately go up to 1.5 M. This is
more than the 1 M CH3COO- can handle (react with). There will still be an excess of H3O+ large enough to bring the
pH down significantly.
In the above case we have overcome the limitations of our buffer and it cannot hold the pH relatively constant any
more.
Buffers only maintain a relatively constant pH when SMALL amounts of acid or base are added to them!

Looking at the “buffer region” of the titration curve for a WA-SB titration illustrates how the buffer “loses control”
of the pH when the [base] overcomes the buffer:
14

12

10

8
pH Point at which the buffer is
Buffer 6 overcome by the base and is
Region unable to minimize the change
4 in pH
2

Uses of Buffers 0
10 20 30 40 50
Volume of Base (mL)
volume (cm³)
Calibration of pH meters
Control of pH in industrial reactions
Used in maintaining water quality
Pools and hot tubs
Wine making
pH balanced shampoos and deodorants
Soil pH
Minimizing effects of acid rain

Biological Buffer Systems

-see p. 182-183 of SW.

For Hemoglobin to work properly, the pH of the blood needs to stay very close to 7.35

Equilibrium: HHb + O2 H 3O + + HbO2-

hemoglobin oxyhemoglobin

When you inhale the [O2] in lungs is high. This diffuses through the thin alveoli walls into the blood. So the
equilibrium above shifts to the RIGHT, producing more oxyhemoglobin.

This “oxygenated” blood then takes the oxyhemoglobin to the cells of the body where [O2] is low. (O2 is used up
during cellular respiration.) Because [O2] is low, the equilibrium shift to the LEFT, releasing O2 to the cells where it
can be used for cellular respiration.

Chemistry 12—Notes on Unit 4 Page 76

Chemistry 12 Notes on Unit 4

This equilibrium must be in a delicate balance for it to work properly.

If [H3O+] is too high (pH too low), the equilibrium cannot shift right enough in the lungs and cannot form enough
oxyhemoglobin. This condition is called acidosis (pH < 7.2)

If [H3O+] is too low (pH too high), the equilibrium cannot shift left enough in the cell and cannot release enough
oxygen. This condition is called alkalosis (pH > 7.5)

Both of these conditions can be deadly.

Buffer Systems in the Blood

CO2 is produced during cellular respiration. It dissolves in the blood and can be thought of as a solution of
“carbonic acid” (H2CO3 ) Also present in our blood stream is “bicarbonate” (HCO3-) which is the conjugate base of
H2CO3. So we have an acidic (WASCB) buffer system in our blood stream:

H2CO3 + H 2O H 3O + + HCO3-

Actually exists
as CO2 & H2O

When the [H3O+] tends to fluctuate in our blood, this buffer maintains the pH as close as possible to 7.35

When a person “hyperventilates”, too much CO2 is lost and this equilibrium shifts to the left, decreasing the [H3O+]
and therefore increasing the pH. This can cause the person to “black out”.

CO2 can be brought back up by “bag breathing” in a paper bag.

Another biological buffer system in the body (this one mainly in cells) is the H2PO4- / HPO42- system:

H2PO4- + H2O HPO42- + H 3O +

weak acid conjugate base

Read though the rather chemically interesting “chicken farmer” exercise 143 on page 183 of SW.

Do Experiment 20-F – Buffers (lab or demonstration depending on time available)

Do “Questions from Provincials for Unit 4”

Test on Unit 4—Acids Bases and Salts.

Chemistry 12—Notes on Unit 4 Page 77