Buffering Regions, Endpoints and Indicators

The endpoint is the

observable colour change.

The equivalence point is

when the amount of acid
and base are precisely
chemically equal.

NO!!
Before any acid titrant is added, the sample solution is mostly water molecules and excess
hydroxide ions.

Buffering occurs because

initially, any acid added
immediately reacts with
the excess hydroxide and
is converted to water.

NO!!
The equivalence point is approached as the excess hydroxide ions in the sample solution
are almost all reacted with the added acid.

Now the solution

consists of water
molecules and excess
hydronium ions.

NO!!
Bromothymol blue is a good indicator to use for a strong acid–strong base titration, because
it changes colour very close to the equivalence point.
 Acid–Base Indicator Equilibrium

An indicator is a Brønstead–Lowry conjugate

weak acid–base pair formed when an indicator
dye dissolves in water.

conjugate pair

HIn(aq) + H2O(l) ↔ In-(aq) + H3O+(aq)

Acid Base
(red litmus) (blue litmus)

An increase in hydronium ions present causes an equilibrium shift to the left, producing
more of the red–coloured acid form.

The presence of excess hydroxide, the hydroxide removes hydronium, producing an

equilibrium shift to the right (blue colour).
 Sample Problem
• Use the following pH scale to label the colors
for bromothymol blue over the 0-14 pH range.
Identify the form of the indicator for each
distinct color using conventional symbols.

0 7 14
Sample Problem: Complete the analysis section
of this investigation.
• Problem: What is the approximate pH (i.e. pH range)
of an unknown solution?
• Evidence: Separate samples of the unknown solution
turned blue litmus to red, congo red to blue and
orange IV to yellow.
• Analysis:
 Sample Problem
• Three unknown solutions in unlabelled
beakers have pH values of 5.8, 7.8, and 9.8.
Write two diagnostic tests using indicators to
identify the pH of each solution.
 Sample Diploma Question
A sample of rain water is poured into five test tubes. A different
indicator is added to each test tube. Four of the observations are
recorded in the table below.
Color
Indicator
Methyl red Yellow
Phenol red Yellow
Bromocresol green Blue
Phenolphthalein Colorless
Bromothymol blue ?

The pH of the rainwater and the predicted color of the sample

containing bromothymol blue are:
A. 6.0 and blue
B. 7.6 and blue
C. 6.0 and yellow
D. 7.6 and yellow
 Sample Diploma Question

Pickling vinegar has a pH of 2.37. When 3 drops of bromocresol green

and 3 drops of phenolphthalein are added to a sample of this vinegar,
the resulting color of the solution is:

A. Yellow
B. Green
C. Blue
D. Purple
 Sample Diploma Question
The labels came off four cleaning solution containers found under a
kitchen sink. Each of the cleaning solutions was tested with two available
indicators and the following results were recorded.

Cleaning Solution Bromothymol blue Phenolphthalein

1 Blue Pink
2 Blue Colorless
3 Green Colorless
4 Blue Light Pink

Listed in order from lowest to highest pH, the cleaning solution are,
respectively,

, , ,and .
(Record your four digit answer in the numerical response section on the
answer sheet)
 Sample Diploma Question
The amphiprotic species that reacts with
bromothymol blue to produce a yellow color
is:
A. NaHSO4(aq)
B. NaHCO3(aq)
C. NaOCl(aq)
D. H2O(l)
 Polyprotic Entities and Sequential Reactions

Na2CO3(aq) → 2 Na+(aq) + CO32–(aq)

The carbonate ion is a

diprotic base because it can
accept two protons.

Hydrochloric acid is a strong

acid, so it is like adding
hydronium ions (H3O+(aq)).
H3O+(aq) + CO32–(aq) → H2O(l) + HCO3–(aq)

H3O+(aq) + HCO3–(aq) → H2O(l) + H2CO3(aq)

 Nitric acid is a monoprotic acid:

HNO3(aq) — NO3–(aq)
1 hydrogen!

Sulfuric acid is a diprotic acid:

H2SO4(aq) — HSO4–(aq) — SO42–(aq)

2 hydrogens!

Remember: for every proton transferred by a polyprotic entity, the strength of the new
acid or base entity formed greatly decreases.
H3PO4(aq) — H2PO4–(aq) — HPO42–(aq) — PO43–(aq)

OH–(aq) + H2PO4– (aq) → H2O(l) + HPO42– (aq)

OH–(aq) + H3PO4(aq) → H2O(l) + H2PO4– (aq)

As a general rule, only quantitative reactions (i.e. 100% reaction) produce detectable
equivalence points in an acid–base titration.
 Sulfuric Acid- A Unique Polyprotic Acid
• Sulfuric acid (H2SO4(aq)) is unique because it is the only strong acid
that is polyprotic, meaning that the first proton lost is already
quantitative in an aqueous solution.
• As a result, its 100% ionization produces hydrogen sulfate ions (HSO4-
(aq)) as well as hydronium ions.
– The hydrogen sulfate ion is the ONLY hydrogen polyatomic that is a weaker
base than water, so it WILL NOT act as a base in aqueous solutions.
– As an acid, however, it will USUALLY react quantitatively with a base
(assuming the base is in excess) in two complete proton transfers.
 Sample Problem
Use the accompanying sketch of a pH curve for a
Acid-Base Reaction
titration to answer the following questions.
1. Does the burette contain the acid or the
base?
2. Is the sample reacted an acid or a base?
3. How many endpoints are represent?
4. Estimate each endpoint.
5. How many quantitative reactions have
occurred?
6. Choose the best indicator for each
endpoint.
7. What part of the curve represents a
possible buffering region?

Volume (mL)
 Read pgs. 751 – 759

 pgs. 754, 755, 759 Practice #’s 1 – 10

 pH Curve Shape versus Acid and Base Strength

Weak acid–weak base titrations do not have a detectable equivalence point, so pH curves
are normally not done for those reactions.
 Strong Base/Strong Acid
H3O+(aq) + OH–(aq) → 2 H2O(l)

• equivalence point is always at a pH of 7

• large vertical portion

• a wide range of indicators would be

useful
 Strong Acid/Weak Base
For example, hydrochloric acid is added to aqueous ammonia:

H3O+(aq) + NH3(aq) → H2O(l) + NH4+(aq)

• equivalence point is always less than

a pH of 7

equivalence point pH = 4.6

• choose an indicator that changes colour at a lower pH value e.g. bromocresol

green
 Strong Base/Weak Acid
For example, barium hydroxide is added to acetic acid:

CH3COOH(aq) + OH–(aq) → H2O(l) + CH3COO –(aq)

equivalence point pH = 9.2

• equivalence point is always greater

than a pH of 7

• choose an indicator that changes colour at a higher pH value e.g. phenolphthalein

 How Buffers Work
• Buffers resist changes in pH if the quantity of excess acid or base added is
less than the quantities of the conjugate pair entities present in the
buffer.
– When an acid is added, the basic entity of the conjugate acid-base pair
neutralizes the acid until consumption is complete and the acid is in excess
resulting in a dramatic pH fall.
– Likewise, when a base is added, the acidic entity of the conjugate acid-base
pair neutralizes the base until consumption is complete and the base is in
excess resulting in a dramatic pH increase.

• Buffering Capacity refers to the limit of the ability of a buffer to maintain

a pH level. When the entity of the conjugate acid-base pair that reacts
with the added reagent is completely consumed. The buffering fails and
the pH changes drastically. (See Figure 16 on p.764)
 pH Curve Buffering Regions and Buffering Solutions

A buffer is a combination of any weak acid with its conjugate base, in the same solution.
(a) OH–(aq) + CH3COOH(aq) → H2O(l) + CH3COO–(aq)

(b) H3O+(aq) + CH3COO–(aq) → H2O(l) + CH3COOH(aq)

Buffer capacity is the limit of the ability of a buffer to maintain a pH level.

Blood plasma is buffered because the chemical reactions that take place in our bodies must be
in a narrow pH range.
 Sample Diploma Question
The main buffer solution of plasma and tissue fluid found in our bodies is
H2CO3(aq) - HCO3-(aq). When excess hydronium ions enter our blood, the
equation that represents the reaction that occurs is:

A. H3O+(aq) + OH-(aq)  2 H2O(l)

B. H2CO3(aq) + OH-(aq)  HCO3-(aq) + H2O(l)
C. H2CO3(aq) + H2O(l)  H3O+(aq) + HCO3-(aq)
D. H3O+(aq) + HCO3-(aq)  H2CO3(aq) + H2O(l)
 Sample Diploma Question

Blood maintain a nearly constant pH because it contains:

A. sodium ions and chloride ions that keep the pH of the blood at 7
B. hemoglobin that maintains the oxygen levels in the blood
C. catalysts (enzymes) that control the equilibrium in the blood
D. buffers that regulate the hydronium ion concentration in the blood
 Sample Diploma Question

Which of the following equimolar solutions could act as a buffer system?

(40% of students got this WRONG on the diploma!)

A. KH2PO4(aq) /H3PO4(aq)
B. KCl(aq)/HCl(aq)
C. KClO4(aq)/HClO4(aq)
D. KNO3(aq)/HNO3(aq)
 Read pgs. 760 – 766

 pgs. 762, 763, 766 Practice #’s 11 – 21

 pg. 767 Section 16.4 Questions 1 – 10
 Acid- Base Stoichiometry
• When completing stoichiometric calculations from titration
evidence, the number of quantitative reactions that occur is
determined by the pH curve. The number of reactions is
equal to the number of protons transferred which, is equal to
the number of endpoints.

• In acid-base stoichiometry two different methods that can be

used to determine the net equation.

1. Using a non-ionic equation

2. Using the method of predicting acid-base reactions
 Method 1: Using a non-ionic equation (double replacement reaction) to determine a
balanced chemical equation

• Method 1 is often simpler and more convenient to use,

however it requires careful consideration of the mole ratio
since polyprotic substances can transfer more than one
proton.

** This method is best if the base can accept ALL protons. For
example, carbonic acid (H2CO3(aq)) reacts with sodium
hydroxide to the second endpoint.
 Method 2: Using the method of predicting acid-base reactions to determine the net
ionic equation

• Method 2 is best used when not all the protons are being
transferred from the acid to the base. For example,
phosphoric acid (H3PO4(aq)) reacts with sodium hydroxide
until a second endpoint is observed.
• However, regardless of the method used, the resulting
equation should be the same!
• The remaining process of solving acid-base stoichiometry
remains the same as with any stoichiometry problem.
 Example

An investigation is preformed to determine the concentration of oxalic acid in a

rust removing solution. Three 10 mL samples of oxalic acid are titrated with a
standardized 1.27 mol/L NaOH(aq) solution. A phenolphthalein indicator is used as
determine the second endpoint. The student collected the following evidence.

Trials
1 2 3
Final buret reading 11.6 23.1 34.5
(mL)
Initial buret reading 0.0 11.6 23.1
(mL)
Volume of NaOH(aq) 11.6 11.5 11.4
added (mL)

Determine the concentration of oxalic acid.

 Solution using Method 1
** 2 endpoints indicate that two protons were transferred. This means that a compound containing the
oxalate ion must be a product.

HOOCCOOH(aq) + 2 NaOH(aq)  Na2OOCCOO(aq) + 2 H2O(l)

To solve:
1. Balance chemical equation including states. List given quantities underneath the appropriate formula.

HOOCCOOH(aq) + 2 NaOH (aq)  2 HOH(l) + Na2OOCCOO(aq)

V= 0.0100 L v= 0.0115L
C =? C= 1.27 mol/L

2. Find number of moles

n = cv
n= (0.0115L)(1.27 mol/L) = 0.0146… mol of OH-(aq)

3. Mole-mole ratio
0.0146 mol of OH-(aq) X 1 mol HOOCCOOH(aq) = 0.00730 mol
2 mol OH-(aq)
4. Solve
C = n = 0.00730 mol = 0.730 mol/L
V 0.010 L
 Solution using Method 2
1st endpoint: HOOCCOOH(aq), Na+(aq), OH-(aq), H2O(l)
SA SS SB A/B
Chemical equation:
HOOCCOOH(aq) + OH-(aq)  HOH(l) + HOOCCOO-(aq)

2nd endpoint: continue to add more strong base

Chemical entities: HOOCCOO-(aq), Na+(aq), OH-(aq), H2O(l)
SA SS SB A/B
Chemical equation:
HOOCCOO-(aq) + OH-(aq)  HOH(l) + OOCCOO 2- (aq)

Net equation:
HOOCCOOH(aq) + OH-(aq)  HOH(l) + HOOCCOO-(aq)
+ HOOCCOO-(aq) + OH-(aq)  HOH(l) + OOCCOO 2- (aq)
HOOCCOOH(aq) + 2 OH- (aq)  2 HOH(l) + OOCCOO2- (aq)

NOTE: When the spectator species from method one (Na +(aq)) is eliminated, both
methods result in the same equation!
 Sample Problem
• A sodium hydrogen phosphate solution is titrated with hydrochloric acid. Only one
quantitative reaction is observed. Sketch the pH curve and provide the relevant
equilibrium equation.
 Sample Diploma Question
• Determine the concentration of phosphoric acid when 10.0 mL is titrated with a
0.250 mol/L potassium hydroxide solution to the second endpoint. The volume of
KOH(aq) that was used to reach this endpoint is 15.0 mL.

(answer: 0.188 mol/L)

 Sample Diploma Question
Use the following information to answer the next two questions
A student titrated a 10.0 mL sample of nitric acid with a 0.00500 mol/L sodium hydroxide
solution in the presence of an indicator. The results were as follows:
Trials
1 2 3 4
Final buret 7.99 14.51 21.02 27.53
reading (mL)
Initial buret 1.00 7.99 14.51 21.02
reading (mL)
Volume 6.99 6.52 6.51 6.51
added (mL)

1. The average volume of titrant used is mL

(Record your answer using three digits)
(answer: 6.51 mL)
Use the recorded value from numerical response 1 to answer numerical response 2.
2. The concentration of the nitric acid is mmol/L
(Record your answer using three digits)
(answer: 3.26 mmol/L)
 Acid- Base Stoichiometry Worksheet
1. In a chemical analysis, 25.0 mL of sulfuric acid is titrated to the
second endpoint with 0.358 mol/L KOH(aq). In the titration, an
average volume of 18.2mL was required. Calculate the molar
concentration of the sulfuric acid. (0.130 mol/L)
2. Several 10.0 mL vinegar samples were titrated with a standardized
0.582 mol/L solution of sodium hydroxide. An average volume of
13.8 mL of sodium hydroxide was required to reach the
phenolphthalein endpoint. What is the concentration of the vinegar
solution? (0.803 mol/L)
3. A sodium borate solution was titrated to the second endpoint with 0.241 mol/L hydrobromic
acid. An average volume of 15.2mL of hydrobromic acid was required to react with 20.0mL samples
of sodium borate. Calculate the molar concentration of sodium borate. (0.0916 mol/L)
4. Complete the analysis for the following investigation report

Problem: What is the concentration of a hydrochloric acid solution?

(answer: 0.179 mol/L)
Experimental Design: 100.0mL of a standard solution of sodium oxalate was prepared using 1.85g
of the dry solid. Using the second endpoint, 10.0mL samples were titrated with hydrochloric acid.
Evidence:

Trials
1 2 3 4
Final buret 16.1 31.5 46.9 16.9
reading (mL)
Initial buret 0.3 16.1 31.5 1.5
reading (mL)
Volume
added (mL)