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R EZI OU A B F C G SL
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D E ZIOU A B F C G H L
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RKP E Z I O U C M F C N X LS
 Carbonic acid-bicarbonate buffer system

• Arterial blood pH is normally closely regulated to

between 7.35 and 7.45

Acidosis < 7.35

Alkalosis > 7.45

• A buffer system functions most effectively when

the concentration of the acid is equal to the
concentration of its conjugate base, pH = pKa

H2CO3 (aq) + H2O (l) ⇋ H3O+ (aq) + HCO3- (aq) Le Chatelier’s principle
weak acid conjugate base
Complex Acid-Base Systems
 Complex acid-base system
• Polybasic acids and polyacidic bases have two or more acidic or basic
functional groups
• monoprotic acid donates one mole of H+ for every one
mole of acid molecules (e.g. HCl, HNO3)

• diprotic acid produces two moles of H+ for every one mole

of acid molecules (e.g. H2SO4)

• triprotic acid donates three moles of H+ for every one

mole of acid molecules (e.g. H3PO4)

• Double indicator titrations

 Common polyprotic acids

Common Number of Ionizable

Formula Strong/Weak Acid Ka1 Ka2 Ka3
Polyprotic Acids Hydrogens

Sulfuric acid H2SO4 Strong 2 (diprotic) Very Large 1.1 × 10-2

Sulfurous acid H2SO3 Weak 2 (diprotic) 1.3 × 10-2 6.2 × 10-8
Phosphoric acid H3PO4 Weak 3 (triprotic) 7.1 × 10-3 6.3 × 10-8 4.2 × 10-13
Carbonic acid H2CO3 Weak 2 (diprotic) 4.4 × 10-7 4.7 × 10-11
Hydrogen sulfide H2 S Weak 2 (diprotic) 1.0 × 10-7 1 × 10-19
Oxalic acid H2 C 2 O 4 Weak 2 (diprotic) 5.4 × 10-2 5.3 × 10-5

Ka1 > Ka2 > Ka3

 Polyprotic acid-strong base titration (H2A – NaOH)

pH H2 A → HA– → A2 –

12 2nd eq pt H2A (aq) + H2O → H3O+ (aq) + HA- (aq) Ka1 =

midpoint 2

Midpoint 1: pH = pKa1 [HA–] = [H2A]

6 1st eq pt
midpoint 1
HA- (aq) + H2O → H3O+ (aq) + A2- (aq) Ka2 =

2
Midpoint 2: pH = pKa2 [A2–] = [HA–]
8 16
Volume of strong base added (mL)

• Multiple equivalence points and buffer regions

• Multiple inflection points in titration curve
 Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...
Step 1 H3PO4 + NaOH → NaH2PO4 + H2O
Step 2 NaH2PO4 + NaOH → Na2HPO4 + H2O
Step 3 Na2HPO4 + NaOH → Na3PO4 + H2O

There are three sharp pH

changes

Each successive addition of

NaOH is the same as equal
number of moles are
involved.
Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...
H3PO4 + H2O ⇋ H2PO4- + H3O+ Ka1 = 7.11 × 10-3

H2PO4- + H2O ⇋ HPO42- + H3O+ Ka2 = 6.32 × 10-8

HPO42- + H2O ⇋ PO43- + H3O+ Ka3 = 4.5 × 10-13

pH of H3PO4 = 1.5
Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...
H3PO4 + H2O ⇋ H2PO4- + H3O+ Ka1 = 7.11 × 10-3

H2PO4- + H2O ⇋ HPO42- + H3O+ Ka2 = 6.32 × 10-8

HPO42- + H2O ⇋ PO43- + H3O+ Ka3 = 4.5 × 10-13

pH of NaH2PO4 = 4.7

pH of H3PO4 = 1.5
Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...
H3PO4 + H2O ⇋ H2PO4- + H3O+ Ka1 = 7.11 × 10-3

H2PO4- + H2O ⇋ HPO42- + H3O+ Ka2 = 6.32 × 10-8

HPO42- + H2O ⇋ PO43- + H3O+ Ka3 = 4.5 × 10-13

pH of Na2HPO4 = 9.8

pH of NaH2PO4 = 4.7

pH of H3PO4 = 1.5
Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...
H3PO4 + H2O ⇋ H2PO4- + H3O+ Ka1 = 7.11 × 10-3

H2PO4- + H2O ⇋ HPO42- + H3O+ Ka2 = 6.32 × 10-8

HPO42- + H2O ⇋ PO43- + H3O+ Ka3 = 4.5 × 10-13

pH of Na3PO4 = 12

pH of Na2HPO4 = 9.8

pH of NaH2PO4 = 4.7

pH of H3PO4 = 1.5
 Double Indicator Titrations
(carbonate and carbonate mixtures)
 Double Indicator Titrations

• In the acid-base titration the equivalence point is known with the help
of indicator which changes its colour at the end point.

• In the titration of poly-acidic base or polybasic acid there are more than
one end point.

• One indicator is not able to give colour change at every end point. So to
find out each end point we have to use more than one indicator.
 Choosing indicators for titration
Strong acid vs. strong base Strong acid vs. weak base Weak acid vs. strong base

acid base
Phenolphthalein colourless pink
Methyl orange red yellow

https://tinyurl.com/y7935ma8
 Double Indicator Titrations
Na2CO3 + HCl
• One indicator is not able to give
colour change at every end point.
So to find out each end point we
have to use more than one
indicator.
n factor
Step 1 HCl + Na CO → NaHCO + H O 1
2 3 3 2

Step 2 HCl + NaHCO → NaCl + CO + H O 2

3 2 2
 Double Indicator Titrations
• Carbonate (CO32–) and bicarbonate (HCO3–) mixture
CO32– , HCO3–

CO32– + H+ → *HCO3-
Vpp

Phenolphthalein endpoint Pink to colourless

Vmo *HCO3– + H+ → H2CO3

HCO3– + H+ → H2CO3

Methyl orange endpoint Yellow to pinkish

• Na2CO3 reacts in both steps using equal volumes of titrant in the two steps. VNa2CO3 = 2 × Vpp

• NaHCO3 reacts only in the second step. VNaHCO3 = Vmo – (2 × Vpp)

 Double Indicator Titrations
Unknown mixture: NaOH + Na2CO3
• NaOH reacts completely in the
OH–, CO32– first step.
OH– + H+ → H2 O VNaOH = Vpp – (Vmo-Vpp)
Vpp
CO32– + H+ → *HCO3–
• Na2CO3 reacts in both steps using
Phenolphthalein endpoint Pink to colourless equal volumes of titrant in the
two steps.
Vmo *HCO3– + H+ → H2CO3
• NaHCO3 reacts only in the second
step.
Methyl orange endpoint Yellow to pinkish
VNa2CO3 = 2 × (Vmo–Vpp)
 Double Indicator Titrations
Relationship between volume of acid needed
Components in the to reach the phenolphthalein end point, (Vpp)
CO32–
sample and methyl orange end point, (Vmo)

Na2CO3 Vpp = ½ Vmo Vpp

NaOH Vpp = Vmo HCO3–

NaHCO3 Vpp = 0, Vmo > 0 Vmo

NaOH, Na2CO3 Vpp > ½ Vmo
CO2
Na2CO3, NaHCO3 Vpp < ½ Vmo

• No more than two of these three constituents can exist in appreciable amount in any solution because
reaction eliminates the third.

• The mixture of NaOH and NaHCO3 is not considered, since these two compounds react:
HCO3 – + OH– → CO32 – + H2O
 Double Indicator Titrations

CO32– CO32–

Vpp Vpp

HCO3– HCO3–

Vmo Vmo

CO2 CO2

Vpp = ½ Vbcg Vpp = Vbcg

Titration curves and indicator transition ranges for the analysis of carbonate
mixtures
 Double Indicator Titrations
Titration curves and indicator
transition ranges for the
analysis of carbonate mixtures

Vpp = ½ Vbcg Vpp = Vbcg

Vpp = 0, Vbcg > 0 Vpp > ½ Vbcg Vpp < ½ Vbcg

 Study Check
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCl. The volumes of acid needed to
titrate separate 25.00mL portions of each solution to a phenolphthalein and
bromocresol endpoint are given in the table that follows. Use this information to
deduce the components in each solution below. Calculate the no. of mg of each
solute per mL of solution.
Solution Volume at phenolphthalein Volume at bromocresol
endpoint (mL) endpoint (mL)
A 22.40 22.40
B 15.71 42.15
C 29.65 36.40
D 16.00 32.00
E 0.00 33.33
 Study Check
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCl. The volumes of acid needed to
titrate separate 25.00 mL portions of each solution to a phenolphthalein and
bromocresol endpoint are given in the table that follows. Use this information to
deduce the components in each solution below. Calculate the no. of mg of each
solute per mL of solution.
Solution Volume at phenolphthalein Volume at bromocresol
endpoint (mL) endpoint (mL)
A 22.40 = 22.40 NaOH
B 15.71 < 1/2 42.15 Na2CO3, NaHCO3
C 29.65 > 1/2 36.40 Na2CO3, NaOH
D 16.00 = 1/2 32.00 Na2CO3
E 0.00 33.33 NaHCO3
 Study Check
A. Given: Vpp = 22.40 mL
Vbcg = 22.40 mL
25.00 mL aliquot
0.1202 M HCl

Need: mg/mL NaOH = ?

Molar mass NaOH

= 22.40 mL HCl × 0.1202 mmol/mL HCl × 40.00 mg NaOH

25.00 mL aliquot mmol

= 4.308 mg/mL NaOH

 Study Check
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCl. The volumes of acid needed to
titrate separate 25.00 mL portions of each solution to a phenolphthalein and
bromocresol endpoint are given in the table that follows. Use this information to
deduce the components in each solution below. Calculate the no. of mg of each
solute per mL of solution.
Solution Volume at phenolphthalein Volume at bromocresol
endpoint (mL) endpoint (mL)
A 22.40 = 22.40 NaOH
B 15.71 < 1/2 42.15 Na2CO3, NaHCO3
C 29.65 > 1/2 36.40 Na2CO3, NaOH
D 16.00 = 1/2 32.00 Na2CO3
E 0.00 33.33 NaHCO3
 Study Check

B. CO32– , HCO3–
Given: Vpp = 15.71 mL
Vbcg = 42.15 mL 15.71 mL CO 2– + H+ → *HCO3-
25.00 mL aliquot 3

0.1202 M HCl Vpp

*HCO3– + H+ → H2CO3
Need: mg/mL Na2CO3 = ? Vbcg = 42.15 mL
mg/mL NaHCO3 HCO3– + H+ → H2CO3
Vbcg

= 2 × 15.71 mL × 0.1202 mmol/mL HCl × 1 mmol Na2CO3 × 105.9888 mg Na2CO3

2 mmol HCl mmol
25.00 mL aliquot

Mole ratio from Molar mass Na2CO3

= 8.006 mg/mL Na2CO3
balanced equation
 Study Check
B. CO32– , HCO3–
Given: Vpp = 15.71 mL
Vbcg = 42.15 mL 15.71 mL CO32– + H+ → *HCO3-
25.00 mL aliquot
0.1202 M HCl Vpp
*HCO3– + H+ → H2CO3
Need: mg/mL Na2CO3 = ? Vbcg = 42.15 mL
mg/mL NaHCO3 HCO3– + H+ → H2CO3
Vbcg

= (42.15 mL – (2 × 15.71 mL)) × 0.1202 mmol/mL × 84.007 mg NaHCO3

25.00 mL aliquot mmol

Molar mass NaHCO3

= 4.334 mg/mL NaHCO3
 Study Check
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCl. The volumes of acid needed to
titrate separate 25.00 mL portions of each solution to a phenolphthalein and
bromocresol endpoint are given in the table that follows. Use this information to
deduce the components in each solution below. Calculate the no. of mg of each
solute per mL of solution.
Solution Volume at phenolphthalein Volume at bromocresol
endpoint (mL) endpoint (mL)
A 22.40 = 22.40 NaOH
B 15.71 < 1/2 42.15 Na2CO3, NaHCO3
C 29.65 > 1/2 36.40 Na2CO3, NaOH
D 16.00 = 1/2 32.00 Na2CO3
E 0.00 33.33 NaHCO3
 Study Check
B. Given: Vpp = 29.65 mL OH–, CO32–
Vbcg = 36.40 mL CO32– + H+ → *HCO3-
29.65 mL
25.00 mL aliquot OH– + H+ → H2 O
0.1202 M HCl
Vpp
Need: mg/mL Na2CO3 = ? Vbcg = 36.40 mL *HCO3– + H+ → H2CO3
mg/mL NaOH = ?
Vbcg
 Study Check
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCl. The volumes of acid needed to
titrate separate 25.00 mL portions of each solution to a phenolphthalein and
bromocresol endpoint are given in the table that follows. Use this information to
deduce the components in each solution below. Calculate the no. of mg of each
solute per mL of solution.
Solution Volume at Volume at Answers
phenolphthalein bromocresol
endpoint (mL) endpoint (mL)
A 22.40 = 22.41 4.308 mg/mL NaOH
B 15.71 < 1/2 42.15 8.006 mg/mL Na2CO3, 4.3333 mg/mL NaHCO3
C 29.65 > 1/2 36.40 3.440 mg/mL Na2CO3, 4.404 mg/mL NaOH
D 16.00 = 1/2 32.00 8.154 mg/mL Na2CO3
E 0.00 33.33 13.46 mg/mL NaHCO3
 SUMMARY
A B

OH–, CO32– CO32– , HCO3–

OH– + H+ → H2 O CO32– + H+ → *HCO3-

Vpp Vpp
CO32– + H+ → *HCO3–

Phenolphthalein endpoint colourless Phenolphthalein endpoint colourless

Vmo *HCO3– + H+ → H2CO3 Vmo *HCO3– + H+ → H2CO3

HCO3– + H+ → H2CO3

Methyl orange endpoint pink Methyl orange endpoint pink

VNaOH = Vpp – (Vmo – Vpp) VNa2CO3 = 2 × Vpp

VNa2CO3 = 2 × (Vmo – Vpp) VNaHCO3 = Vmo - 2Vpp

 References
• Douglas A. Skoog, Donald M. West, F. James Holler, and Stanley R.
Crouch. 2013. Fundamentals of analytical chemistry, 9th ed.,
Brooks/Cole, Cengage Learning.

• Harris, D.C. 2015. Quantitative Chemical Analysis. International

Edition. New York: W.H. Freeman and Co., New York.
 Announcements
• First Long Exam
When: 30 October 2020
Time: 3:00 – 5:00 pm
Duration: 2 hours
Type of Exam: Problem solving
Coverage: Modules 1-6
Total Points 100 pts
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• Mid-semester break 02-06 November 2020

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