Equilibrium constants in electrolyte solution, pH and titration

Equilibrium constants for chemical reactions :

a. Acids and bases – axit bazo
b. Complex formation – tạo phức
c. Solubility product, Precipitation reaction – kết tủa
d. Redox reaction, standard electrode potential – oxy hoá khử
AQUEOUS EQUILIBRIA
Acids and Bases equilibria

• Arrhenius Definitions－Acids produce hydrogen ion in

aqueous, and bases produce hydroxide ions.
• Brønsted-Lowry Definitions－An acid is a proton (H+)
donor, and a base is a proton acceptor.
 Nomenclature – Thuật ngữ
English
1 Mono, di- tri- protic acid
2 lone pair of electron
3 Acid/base dissociation
constant
4 Conjugate acid-base pair
5 Complexation reaction
6 Precipitation reaction
7 Redox reaction
8 Mass/charge balance
9 Titration, titrant
10 Equivalent point, end point
Tiếng Việt
Axit 1 lần, 2 lần, 3 lần axit
Cặp điện tử tự do
Hằng số phân ly axit, bazo
Cặp axit-bazo liên hợp
Phản ứng tạo phức
Phản ứng tạo kết tủa
Phản ứng oxi hoá – khử
Bảo toàn khối lượng, điện tích
Chuẩn độ, chất chuẩn
Điểm tương đương, điểm cuối
Brønsted-Lowry Definitions
 Introduction: Solutions

Heterogeneous mixture: ununiform composition Solution: small particles & transparent

Homogeneous mixture: uniform composition Colloid: larger particles & opaque
Introduction: Solutions

When two substances form

a solution, the substance
present in the lesser
amount is called the solute,
and the substance present
in the larger amount is the
solvent.
A solution with water as the
solvent is called an aqueous
solution.
 Concentration
1. Weight/volume percent concentration and Volume/Volume percent concentration
Number of grams of solute in 100 ml solution
C (%) = mass of solute (gram)/volume of solution (ml).
Example, vinegar contains 5 g of acetic acid dissolved in 100 mL of solution, so the acetic acid concentration is
5% (w/v).

2. Molarity concentration (M). Mol/liter

Number of mole of solute in 1 liter of solution
C (%) = moles of solute/liter of solution (L)

3. Part per million, part per billion concentration (ppm; ppb; ppt)

1 ppm = 1 mg/L = 1 mg/kg

1 ppb = 1 µg/L = 1 µg/kg

1 ppt = 1 ng/L = 1 ng/kg

A general Brønsted–
Lowry acid is
often written as HA. A
can be a single atom,
polyatomic ions,
carboxylic acids
Example: HCl, H2SO4,
CH3CHOOH
Bronsted-Lowry Acids
Examples of
Bronsted-
Lowry acids
in food
products
Bronsted Lowry Base

Base is a proton receptor, it should be able to form a bond to H+,

should contain a lone pair of electron
 Examples of Bronsted Lowry Base
Hydroxide (–OH), which contains an oxygen atom with three lone pairs of electrons, is the most common
Brønsted–Lowry base. The source of hydroxide anions can be a variety of metal salts, including NaOH, KOH,
Mg(OH)2, and Ca(OH)2.
Examples of bases in consumer products
 Proton transfer: reaction of a acid and a base
When a Brønsted–Lowry acid reacts with a Brønsted–Lowry base, a proton is transferred from the acid to the base. The
Brønsted–Lowry acid donates a proton to the Brønsted–Lowry base, which accepts it.
Example, the reaction of the general acid H A with the general base B:.
In an acid–base reaction, one bond is broken and one bond is formed. The electron pair of the base
B: forms a new bond to the proton of the acid, forming H B+. The acid H A loses a proton,
leaving the electron pair in the H A bond on A, forming A:–.

Two species that differ

by the presence of
A proton H+ are called
a Conjugate acid-base
pair
Cặp axit-bazo liên hợp
Acid dissociation constant KA & Base dissociation constant KB
Equilibrium constant for the acid–base reaction that takes place when an acid HA dissolves in water. The
equilibrium constant (K) shows the ratio of the concentrations of the products to the concentrations of
the reactants
• Dissociation of acid, Ka

Stronger acid: larger value of KA

Stronger base: larger value of KB
• Dissociation of base, Kb
 Examples of Acid dissociation constants
Acid Formula Ka Acid Formula Ka
Acid
Dissociation
Hydroflouric HF 7.1×10-4 Hydrocyanic HCN 4.9×10-10 Constant (Ka)
Values at 25 oC

Formic HCOOH 1.7×10-4 Carbonic H2CO3 4.2×10-7

4.8×10-11

Lactic H3CCH(OH)C 1.4×10-4 Phosphoric H3PO4 7.5×10-3

OOH 6.2×10-8
4.8×10-13
Benzoic C6H5COOH 6.5×10-5 Oxalic H2C2O4 6.5×10-2
6.46×10-5

Acetic H3CCOOH 1.8×10-5 Hypochlorous HOCl 3.0×10-8

• Ka, Kb are constant at a certain temperature and pressure.

• Ka, Kb represent the strength of acid and base.

The smaller the Ka (Kb) : the weaker the acid (base).

• Strong acid (HCl, HNO3); weak acid: carboxylic acid

• Strong base, weak base: amine

• Monoprotic acid: one acidic proton, HCl, HNO3, CH3COOH

• Monoprotic base: NaOH, NH4OH

• Polyprotic acid: more than one acidic proton, H3PO4, H2SO4

• Polyprotic base: Cu(OH)2, Fe(OH)3,..

 Dissociation of water and pH
• Dissociation of water

• Water dissociation coefficient

• Kw varies with temperature, at 200C Kw = 6.809×10-15;

at 300C Kw = 1.469×10-14
• pH = -log[H+] ; pOH = -log[OH-] (ignoring activity correction)
• pH + pOH = 14 (to the extent that Kw = 1×10-14)
• For neutral solution: pH =pOH =7 (at 250C)
• Acidic solution: pH < 7; basic solution: pH >7
Ka,Kb of conjugate acid/base pair
Dissociation of CH3COOH
CH3COOH + H2O « CH3COO- + H3O+ (1) Ka
CH3COO- + H2O « CH3COOH + OH- (2) Kb
(1) + (2) gives:
2H2O « H3O+ + OH-
So KaKb =Kw = 10-14
Or pKa + pKb = 14.
* Example: Ka,CH3COOH = 10-4.75 ; Find Kb, CH3COO- =?
Kb,NH3 = 10-4.75 , Find Ka,NH4+ = ?
COMPLEXATION REACTION/EQUILIBRIUM

Metal ion Ligand Metal-ligand complex

• Formation constant Kf:

• (stability constant)
• Meaning of Kf: stability of the complex, the larger the Kf, the more
stable the complex.
• When reaction occurs in several steps,
use Ki (stepwise formation constant) for stepwise reaction
and bI (cumulative formation constant) for overall reaction.
 Stepwise formation constant
K1

K2

K3

K4

Cumulative formation constant

b4 = K 1 K 2 K 3 K 4

Cd2+ (aq) + n:NH3(aq) « Cd(:NH3)n2+ (aq) bI = K1K2..Ki

 PRECIPITATION REACTION/EQUILIBRIUM
• Formation of precipitate from soluble species:

• Solubility product

• Meaning of Ksp:
• The smaller the solubility product, the more difficult the precipitate is to
dissolve.
• Able to calculate the concentrations of ions in equilibrium with precipitation =
solubility (S)
• When does precipitation form or dissolve?
• If [Pb2+][Cl-]2 > Ksp, PbCl2 à precipitation forms
• [Pb2+][Cl-]2 < Ksp, PbCl2 à precipitation does not form; if solid (in excess) is in
contact with an aqueous solution à dissolves.
Solubility Product Table

Salt Ksp Salt Ksp Salt Ksp

Bromides Carbonates Oxalates

PbBr2 6.6 × 10-6 MgCO3 6.8 × 10-6 MgC2O4 4.8 × 10-6

CuBr 6.3 × 10-9 NiCO3 1.3 × 10-7 FeC2O4 2 × 10-7

AgBr 5.4 × 10-13 CaCO3 5.0 × 10-9 NiC2O4 1 × 10-7

Hg2Br2 6.4 × 10-23 SrCO3 5.6 × 10-10 SrC2O4 5 × 10-8

Problem:
The Ksp for AgCl is 1.8 × 10-10. If Ag+ and Cl- are both in solution
and in equilibrium with AgCl, what is [Ag+]
if [Cl-] = 0.020 M?

If Ag+ and Cl- were both present at 0.0001 M, would a

precipitate form (would precipitation occur)?

What concentration of Ag+ would be necessary to bring the

concentration of Cl- to 1.0 × 10-6 M or lower?
How to calculate concentrations of species in a solution at equilibrium

Find concentrations of species in a solution, say, solution of NH3 1M?

Charge balance and mass balance

• Charge balance equation

Total charge from cations equal to the total charge of anions.
Exp: Solution of Ca(NO3)2
H2O « H+ + OH-
Ca(NO3)2 à Ca2+ + NO3-
2x[Ca2+] + [H+] = [NO3-] + [OH-]
• Solution of KH2PO4 ?
 Mass balance equation

• The quantity of all species in a solution containing a particular atom (or

group of atoms) must equal the amount of that atom (or group) delivered
to the solution.

• Exp: Dissolve 0.050 mol CH3COOH into 1.00 L water.

• CH3COOH « CH3COO- + H+
Mass balance for CH3COOH:
Cinitial = 0.050M = [CH3COOH] + [CH3COO-]
What put into Undissociated Dissociated
the solution product product
Apply to solve equilibrium- how calculate pH of electrolyte solutions

pH of strong acid and strong base

Strong acid HA with initial concentration Ca
HA à H+ + A-
Since HA is completely dissociated, H+ concentration is considered to be mainly from HA.
[H+] = Ca
Similarly, strong base BOH with initial concentration Cb
BOH à B+ + OH-
[OH-] = Cb

Example: pH of HCl 0.1 M. [H+] = Ca = 0.1 M, pH = -log (0.1) = 1

pH of NaOH 0.1 M. [OH-] = Cb = 0.1 M, pOH = -log (0.1) = 1, pH = 14-1=13.
• pH of weak acid: [H+] = √KACA
• pH of weak base: [OH-] = √KbCb

• Salt of strong acid and weak base: weak acid

NH4Cl is salt of HCl (strong acid) and weak base (NH3), is a weak Acid. [H+] = √KaCa

• Salt of strong base and weak acid: weak base

CH3COONa is salt of NaOH (strong base) and CH3COOH (weak acid),
is a weak base [OH-] = √KbCb
pH of amphoteric salt (both acid & base properties)

Salt of di- or triprotic acid: H2CO3, H3PO4

H2CO3 ⇌ H+ + HCO3- K1 = 4.2×10-7
HCO3- ⇌ H+ + CO32- K2 = 4.8×10-11
pH of NaHCO3 . [H+] = √K1K2

H3PO4 ⇌ H2PO4- + H+ K1 = 10-2.12

H2PO4- ⇌ HPO42- + H+ K2 = 10-7.21
HPO42- ⇌ PO43- + H+ K3 = 10-12.36

pH of H2PO4- (e.g. NaH2PO4). [H+] = √K1K2

pH of HPO42- (e.g. Na2HPO4). [H+] = √K2K3
 Buffer solution

• Definition: solution resist pH changes when acids and bases are

added or dilution occurs.
• Mixture of an acid and its conjugate base.
• For example: CH3COOH/CH3COONa
• The concentrations of HA and A- remain almost unchanged when
they are mixed
• [HA] and [A-] changes when solution is too dilute or at extreme pH.
Henderson-Hasselbalch equation (pH of buffer solution)

For buffer solution of acid

For buffer solution of base

Practical knowledge: variation of pH in human body

ü The pH of some body fluids must occupy a

very narrow range. For example, a healthy
individual has a blood pH in the range of
7.35–7.45.
ü The pH of other fluids can be more
variable. Urine has a pH anywhere from
4.6–8.0, depending on an individual’s
recent diet and exercise.
Tools for Measuring pH
 Practical knowledge: Application of buffers

l Keep the correct pH for enzymes in many organisms to work;

l In industry, buffer solutions are used in fermentation processes and in setting
the correct conditions for dyes used in coloring fabrics.
l In chemical analysis, calibration of pH meters.
l Biological buffers: most of biological samples have to been made in buffers,
especially phosphate buffered saline (PBS) at pH 7.4.
l Blood : A buffer of H2CO3/HCO3-, maintain pH from 7.35 to 7.45.
pH of some common substances
 Buffer capacity

l Buffer capacity: ability to resist a change in pH when adding a strong base or

strong acid
l The higher the concentration of buffer, the larger the buffer capacity
l (however, don’t use too high concentration, to avoid precipitate and limited
solubility of salt, to avoid ion pairing, and to avoid activity coefficient changes)
l The closer the pH of buffer to the pKa, the higher the buffer capacity; maximum
at pH = pKa
l “Rule of thumb” to prepare good buffer: Choose reagents with pKa close to the
desired pH.
How to prepare buffers?

l Practically:
- Use standard recipe from literature
- or use computer program to calculate the composition of buffer.
- The most common way:
- Prepare solution of an acid and its conjugate base (with appropriate pKa)
- Measure pH
- Adjust pH to the desired pH by adding a small portion of
acid or base
 "Universal" buffer mixtures

0.2M Na2HPO4 /mL 0.1M Citric Acid /mL pH...

20.55 79.45 3.0
38.55 61.45 4.0
51.50 48.50 5.0
63.15 36.85 6.0
82.35 17.65 7.0
97.25 2.75 8.0
Practical knowledge: Buffers in the human blood

ü The normal blood pH of a healthy individual is in the range of 7.35 to 7.45. A pH

above or below this range is generally indicative of an imbalance in respiratory or
metabolic processes.
ü The body is able to maintain a very stable pH because the blood and other tissues
are buffered.
ü The principal buffer in the blood is carbonic acid/bicarbonate (H2CO3/HCO3–).
 Carbonic acid (H2CO3) is in equilibrium
with CO2 dissolved in the bloodstream
Since carbonic acid is a weak acid, it is
also dissociated in water to form its
conjugate base, bicarbonate (HCO3).
Bicarbonate is also generated in the
kidneys

CO2 is constantly produced by metabolic processes in the body and transported to the lungs to be eliminated. The
amount of CO2 dissolved in the blood is directly related to the H+ concentration and therefore the pH of the blood. If the
pH of the blood is lower than 7.35, the blood is more acidic than normal, and the condition is called acidosis.
If the pH of the blood is higher than 7.45, the blood is more basic than normal, and the condition is called alkalosis.
Le Châtelier’s principle explains the effect of increasing or decreasing the level of dissolved CO2 on the pH of the blood. A
higher-than-normal CO2 concentration shifts the equilibrium to the right, increasing the H+ concentration and lowering
the pH. Respiratory acidosis results when the body fails to eliminate adequate amounts of CO2 through the lungs. This
may occur in patients with advanced lung disease or respiratory failure.
Which is the principal species at certain pH?
Titration
Phương pháp chuẩn độ

Lecturer: Tu Binh Minh

VNU Hanoi University of Science
 Titration

• Titration is a common laboratory method of quantitative

chemical analysis that is used to determine the unknown
concentration of a known reactant by measuring volume
of standard solution.
• Because volume measurements play a key role in
titration, it is also known as volumetric analysis.
 Terminology
• Standard solution is a chemical term which describes a solution of known
concentration.
• Concentration
1. Mass conc (conc. in g.dm-3 ) :Mass (in grams) of a substance dissolved in
1dm-3 of solution.
2.Molarity (conc. in mol.L-1) used to calculate # of mole of substance in the
reactions
* Equivalence point: when reactants finish reacting together (in
theory)
• End point - the titration is stopped (in reality)
• Steep rise interval; range of titration curve when pH suddenly
changed
 Titration
- A method for determination of a chemical (acid, base, ions, reduction/oxidation agents …)
based on the measurement of Volume of a standard solution in a complete quantitative
reaction
- A titration uses a burette, a calibrated tube with a stopcock at the bottom that allows a
solution of known molarity to be added in small quantities to a solution of unknown molarity.
A titration is based on the acid–base reaction that occurs between the acid in the flask
(HCl) and the base that is added (NaOH). When the number of moles of base added
equals the number of moles of acid in the flask, the acid is neutralized, forming a salt
and water.
 Example: acid rain’s rainwater titration
Acid rain is rainwater with a lower-than-normal pH, caused by the presence of dissolved acids such as
H2SO4. What is the molarity of H2SO4 in rainwater if 5.22 mL of a 0.20 M NaOH solution are needed to titrate
125 mL of the sample?
H2SO4(aq) + 2 NaOH(aq) = Na2SO4(aq) + 2 H2O(l)
 Finding the end point with indicator
l Acid-base indicator: organic weak acid (or base) which has
color changing with pH.

l The basic form and the acidic form of the indicator have
different colors HInd « H+ + Ind-

(yellow) (red)

l If [HInd] = 10x [Ind-]

l If [Ind-] = 10x[HInd]
Finding the end point with indicator

Species H3Ind+ H2Ind (Lacton) Ind2− (Quinon) Ind(OH)3−

Structure

pH <0 0−8.2 8.2−12.0 >13.0

acidic or near-
Conditions strongly acidic basic strongly basic
neutral
Color orange colorless pink to fuchsia colorless

Image
Indicator for acid-base titration
Common acid-base Indicators
 Curve represents relationship of pH of the
Titration curve solution and volume of Standard added

Concentration of standard: C
(known)
Volume of standard: V (will know at
the end point)

Concentration of analyte: Co
(unknown)
Volume of analyte Vo (Known)

At the equilibrium point:

CV = CoVo
-> Co = CV/Vo
 How to Choose indicators

- The indicator’s pH range (transition range) must fall within the rapid
change of pH (step) at equivalence point (steep rise interval of the
titration curve)
- The closer the pH of color change to the pHeq à the more accurate
the end point.
- Difference between end point (color change) and equivalence point:
indicator error.
- Use indicators as little as possible since they are acids or bases and will
react with your analyte.
steep rise
interval of
the titration
curve
 Features of the Strong Acid-Strong Base
Titration Curve
1. The pH starts out low, reflecting the high [H3O+] of the
strong acid and increases gradually as acid is neutralized by
the added base.
2. Suddenly the pH rises steeply. This occurs in the immediate
vicinity of the equivalence point. For this type of titration
the pH is 7.0 at the equivalence point.
3. Beyond this steep portion, the pH increases slowly as more
base is added.
 HPr = Propionic Acid
HA + NaOH = NaA + H2O

1.Region 1: Before the equilibrium point

Solution contains A- and HA: buffer solution
pH = pKa + log(Cb/Ca)
2.Region 2: At the equilibrium point
Solution contains only A-: salt of strong base and weak acid
It is a weak base. [OH-] = √KbCb
3. Region 3: After the equilibrium:
Solution A- and NaOH excess. pH calculate as strong base
[OH-] = CNaOH excess
Major Differences Between a Strong Acid-Strong Base Titration
Curve and a Weak Acid-Strong Base Titration Curve

1. The initial pH is higher.

2. A gradually rising portion of the curve, called the
buffer region, appears before the steep rise to the
equivalence point.
3. The pH at the equivalence point is greater than 7.00.
4. The steep rise interval is less pronounced.
Selected primary Standards for Standardizing strong acid and
strong base titration
 Complexation Titration
Chuẩn độ tạo phức (complexon)
Complex-formation reactions are widely used in analytical chemistry.
- Applications for titrating cations: determination of cations
Complexometric titrations: a metal ion reacts with a suitable ligand to form a complex, and the
equivalence point is determined by an metallic indicator or a suitable instrumental method.
Reagents for EDTA Titrations: Standard
EDTA: ethylene diamine tetra acetic acid
Na2H2Y.2H2O (trilon B) is used as a primary standard;
can be prepared by drying at 80oC for several days
in an atmosphere of 50% relative humidity.

Titration reaction: Mn+ + Y4- = MY(n-4)

Molarity ratio between metal ion and EDTA is always 1 : 1
Example: Mg2+ + Y4- = MgY2-
Al3+ + Y4- + AlY-
 Indicators for EDTA Titrations - chất chỉ thị cho chuẩn độ EDTA

Indicators are organic dyes that form colored chelates with metal ions in a pM range
that is characteristic of the particular cation and dye. The complexes are often
intensely colored and are discernible to the eye at concentrations in the range of 10-6
to 10-7 M.
Eriochrome Black T is a typical metal-ion indicator used in the titration of several
common cations.
H2In- (red) « HIn2- (blue) + H+ K1 = 5 x 10-7
HIn2- (Blue) « In3- (orange) + H+ K2 = 2.8 x 10-12
The acids and their conjugate bases have different colors.
When pH < 6,3 solution is red
pH >11,5 Solution is orange
6.3 < pH < 11.5 Solution is blue.
 Mechanism of color change at the equilibrium point

• Color of indicator ETOO is different from color of complex of Metal and indicator (M-
Ind)
• ETOO: blue color. When complex with Metal ion (M) produce complex: ETOO-Mg:
red color
• During titration process:
– Before equilibrium: M + ETOO = M-ETOO (red) M-ETOO: red color
– After equilibrium:
M-ETOO + EDTA = ETOO (blue) + M-EDTA ETOO: blue color
At the equilibrium: the color of the solution changes from red to blue.
Metal Ion Indicator Compounds
 Complexation Titration Curve

Titration curve: a plot of pM = -log[M] as a function of

the volume of titrant added. [M]: concentration of metal
ion at equilibrium
EDTA: standard

ETOO: indicator

Metal ions (M): analyte

 Effect of pH in the titration
curve in EDTA titration

Titration of Ca2+ by EDTA:

Steep rise interval high at
higher pH values because
complexes between Ca2+ and
EDTA are stable at higher pH
Effect of stability constant K of
complexes in the titration curve
in EDTA titration. More stable
complexes with higher K values
give better titration (greater
steep rise intervals)
Relationship between pH and K of
complexes of different cations

Fe, Th, Hg: acidic medium

Ca, Mg, Sr: base medium
Others: neutral medium
Titration based on Redox reaction
 The shape of a redox titration curve
• A redox titration is based on an oxidation-reduction reaction
between analyte and titrant.
• Consider the titration of iron(II) with
standard cerium(IV), monitored
potentiometrically with Pt and
calomel electrodes.

The potentials show above is in 1 M HClO4

solution. Note that equilibria 16-2 and 16-3
are both established at the Pt electrode.
• There are three distinct regions in
the titration of iron(II) with
standard cerium(IV), monitored
potentiometrically with Pt and
calomel electrodes.
1. Before the equivalence point,
where the potential at Pt is
dominated by the analyte redox
pair.
2. At the equivalence point, where
the potential at the indicator
electrode is the average of their
conditional potential.
3. After the equivalence point, where
the potential was determined by
the titrant redox pair.
A redox titration is feasible if
the difference between
analyte and titrant is > 0.2 V.

If the difference in the formal

potential is > 0.4 V, then a
redox indicator usually gives
a satisfactory end point.
 Oxidation with potassium permanganate

• KMnO4 is a strong oxidant with an intense violet color. In strongly

acidic solutions (pH < 1), it is reduced to Mn2+.
• In neutral or alkaline solution, it is reduced to brown solid MnO2.
• In strongly alkaline solution ( 2 M NaOH), green manganate ion
(MnO42-) is produced.
• Titration reaction in strong acidic medium:
MnO4- + 8H+ + 5e = Mn2+ + 4H2O
Standard redox potential Eo = + 1.52 V
Dichromate titration method
Example of dichromate method