11

General Chemistry 2
Quarter 4 – Module 1-3
 Development Team of the Module

Writers: CHARISMA M. FERRER, TIII

MARY ANN M. GUEVARRA, TIII
MADONNA L. MADRIDANO, MTI

Consolidator: CHARISMA M. FERRER

Language Editor: AMALIA A. MANLAPAO

Content Validators: MARIEL B. BARAGENIO

REX S. LAPID
MARITES T. TUDIO

Cover Page Illustrator: AIRA MARI CON M. AUSTERO

Team Leader: DR. RACQUEL M. AUSTERO

Education Program Supervisor

2
 R epublicof the P hilippines
D epartment of Education
N a t i o n a l C a pi t a l Re g i o n
Sc h o o l s D i v i s i o n O f f i c e o f La s Pi ñ a s C i t y

Module in General Chemistry 2

Grade 11
Fourth Quarter
Week 1

MOST ESSENTIAL LEARNING COMPETENCIES

• Predict the spontaneity of a process based on entropy (STEM_GC11CT-IVa-b-140)
• Explain the second law of thermodynamics and its significance (STEM_GC11CT-
IVa-b-142)
• Use Gibbs’ free energy to determine the direction of a reaction (STEM_GC11CT-
IVa-b-143)

WHAT’S IN

Spontaneous Processes
A spontaneous process is a process that occurs under a specific set of conditions. This
process occurs without an outside force and continues until it is in equilibrium.

Examples:
• Heat flows from a hotter object to a colder one
• An iron object rusts in moist air
• Sugar dissolves in a cup of coffee

How does spontaneity apply to chemical reactions?

In a chemical reaction,
ΔHreaction = Hproducts - Hreactants.
For an exothermic reaction:ΔHreaction = negative (-).

A spontaneous process takes place without intervention or force from an outside source.
Without a source of energy, a spontaneous reaction will proceed from left to right.

3
Examples of reactions that are very exothermic and are not reversible:
• Combustion of methane
CH4 + 2O2 —> 6CO2 + 2H2O ΔHo = - 890.4 kJ/mol

• Acid-base neutralization reaction

H+(aq) + OH- (aq) —> H2O (l) ΔHo = - 56.2 kJ/mol

Examples of spontaneous process yet endothermic reactions:

• Solid to liquid phase transition of water
H2O (s) —> H2O (l) ΔHo = 6.01kJ/mol

• Dissolution of ammonium nitrate in water

NH4NO3 (s) —> NH4 + (aq) + NO3 - (aq) ΔHo = 6.01 kJ/mol

Entropy
• Entropy, S, is a thermodynamic quantity.
• It is used to measure how spread out or dispersed the energy of a system is.
• It is used to describe if the process is spontaneous and can occur in a defined
direction or non-spontaneous and will occur in the reverse direction.
• It is considered as a state function.
• The SI unit of entropy is Joules per Kelvin (J/K)
• It is also a measure of how random or disorder the system is.

The following processes result to an increase in entropy of the system.

Process Order → Disorder
Melting Solid → Liquid
Vaporization Liquid → Vapor
Dissolving Solute → Solution
Heating System @ T1 → System @ T2 (T2>T1)

The spreading out of more concentrated molecules and energy is a change from more
order to more random system. This change led to an increase in the randomness of the
universe.

4
 Figure 1. heat (direction of heat flow)
http://www.physchem.co.za/Heat/Effects.htm

In the illustration above, the spontaneous process occurs from solid to liquid to gas. Solid
is less random than liquid and liquid is less random than gas. The change from solid to
liquid to gas leads to an increase in entropy of the system.

Patterns in the entropies of substances

excerpts from the Thermodynamics Table

https://www2.chem.wisc.edu/deptfiles/genchem/netorial/modules/thermodynamics/entro
py/entropy06.htm

The entropies of solids are smaller than those of liquids and the entropies of gases are
larger than the entropies of liquids. Gases have the highest entropies among solids,
liquids, and gases.

The arrangement of atoms in solids, liquids, and gases explains why gases have the
highest entropies. The atoms in solids are compact and can only vibrate that’s why small
entropies while the atoms in liquids are not that far and so they are free to move thus,
they are more random and the atoms in gases are very far from each other and so they
are more random and disordered.

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In column 3, complex molecules have greater entropies than simple molecules.
Complicated molecules are more random because of greater probability that they can be
arranged and moved around in three-dimensional space.

In columns 5 and 7, entropies of ionic solids are greater if the bonds are weaker. Weaker
bonds will not hold the atoms in place unlike stronger bonds. Thus, weaker bond will
cause more disorder and greater entropy.
Two more patterns emerge from considering the implications of the first three.

When a liquid or solid dissolves in a solvent, entropy usually increases. When the solute
and solvent are mixed, they are completely distributed and so entropy increases.

When a gas dissolves in a liquid or solid, entropy is usually decreased. This is because
more mixing is involved and the atoms of gas become closely packed from being very far
from each other.

Trends in Entropy:

• Entropy for gas phase is greater than that of liquid or solid of same substance
Ssolid < Sliquid << Sgas
I2 (g) has greater entropy than I2 (s)
• More complex structures have greater entropy
C2H6 (g) has greater entropy than CH4 (g)
• Spure < Saqueous
• Slower temp < Shigher temp
• Sfewer moles < Smore moles
• Standard entropies tend to increase with increasing molar mass.
Larger and more complex molecules have greater entropies (greater ways to execute
molecular motions)

Entropy and the Second Law of Thermodynamics

The second law of thermodynamics explains the relationship between entropy and the
spontaneity of natural processes. It tells whether a process or chemical reaction will
proceed. It states that: “The entropy of the universe increases in a spontaneous process
and remains unchanged in an equilibrium process.” Since the universe is composed of
the system and the surroundings, the change in entropy of the universe (ΔSuniv) for any
process is equal to the entropy changes in the system (ΔSsys) plus the entropy change in
the surroundings (ΔSsur). Mathematically,
ΔSuniv = ΔSsys + ΔSsur > 0 Process is spontaneous.
ΔSuniv = ΔSsys + ΔSsur = 0 Process tends not to occur; equilibrium is attained.
ΔSuniv = ΔSsys + ΔSsur < 0 Reverse process occurs spontaneously.

Calculating Entropy Changes in the System: Standard Entropy of Reaction, ΔS°rxn

ΔS° = ΣnS° (products) − ΣmS° (reactants)
• Where m and n are the stoichiometric coefficients in the reaction.

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Example: From the standard entropy values in the Thermodynamic Data table, calculate
ΔS° for the following reaction.
H2(g) + I2(s) —> 2HI(g)
From the table,
H2(g) + I2(s) —> 2HI(g)
S°(J/K·mol): 130.6 116.7 206.3
ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(2) So HI] – [(1) So H2 + (1) So I2]
= [ (2) (206.3) ] – [ (1) (130.6) + (1) (116.7) ] = [ 412.6 ] – [ 247.3 ]
ΔS° = +165.3 J/K

Practice Problem 1: (Adapted from General Chemistry 2 Module)

Predict whether the entropy change of the system in each of the following is positive or
negative.
1) N2 (g, 10 atm) —> N2 (g, 1atm).
2) 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g).
3) 2 H2 (g) + O2 (g) —> 2 H2O (l)
4) NH4Cl (s) —> NH3(g) + HCl (g)

Solution:
1) N2 (g, 10 atm) —> N2 (g, 1atm). Positive
Decrease in pressure of the system will increase entropy

2) 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g). Negative

Decrease in number of gas particles

3) 2 H2 (g) + O2 (g) —> 2 H2O (l) Negative

Net decrease in number of molecules and gases are converted to solids

4) NH4Cl (s) —> NH3(g) + HCl (g) Positive

A solid is converted to two gaseous products.

Practice Problem 2: (Adapted from General Chemistry 2 Module)

1. Determine S for the reaction:

SO3(g) + H2O(l) —> H2SO4(l)
Given: S°(J/K·mol): 256.2 69.9 156.9

2. Calculate S for the reaction

SO2(s) + NO2(g) —> SO3(g) + NO(g)
Given: S°(J/K·mol): 248.5 240.5 256.2 210.6

3. Calculate S at 25C for the reduction of given these absolute entropies:

2PbO(s) + C(s) —> 2Pb(s) + CO2(g)
Given: S°(J/K·mol): 69.54 5.7 64.89 213.6

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Solutions:
1. ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(1) So H2SO4] – [(1) So SO3 + (1) So H2O]
= [(1) (156.9) ] – [ (1) (256.2) + (1) (69.9) ]
ΔS° = -169.2 J/K·mol

2. ΔS° = ΣnS° (products) − ΣmS° (reactants)

= [(1) So SO3 + (1) So CO2] – [(2) So SO2+ (1) So NO2]
= [(1) (256.2) + (1)(210.6)] – [ (1) (248.5) + (1) (240.5) ]
ΔS° = -22.2 J/K·mol

2. ΔS° = ΣnS° (products) − ΣmS° (reactants)

= [(2) So Pb + (1) So CO2] – [(2) So PbO + (1) So C]
= [(2) (64.89) + (1)(213.6)] – [ (2) (69.54) + (1) (5.7) ]
ΔS° = +198.6 J/K·mol

Calculating the Entropy Changes in the Surroundings, ΔSsur

Change in entropy of surroundings is directly proportional to the enthalpy of the system.
Ssurroundings  − Hsystem
Where:
Ssurroundings = entropy of the surroundings
Hsystem = enthalpy of the system

Change in entropy of surroundings is inversely proportional to temperature

Ssurroundings  1 / T
Where:
T = temperature
Therefore:
− 𝐻system
ΔSsur = 𝑇

Example: Is the reaction spontaneous at 25 oC?

N2 (g) + 3 H2 (g) —> 2 NH3 (g) ΔH°rxn = - 92.6 kJ/mol
− 𝐻system
ΔSsur = 𝑇

= − (− 92.6 kJ/mol)(1 kJ/1000 J) /298 K

ΔSsur = 311 J/K ·mol

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 ΔSsystem:
From the table,
N2 (g) + 3 H2 (g) —> 2 NH3 (g)
S°(J/K· mol): 192 131 193
ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(2) So NH3] – [(1) So N2 + (3) So H2]
= [ (2) (193) ] – [ (1) (192) + (3) (131) ]
ΔS° = −199 J/K· mol

Determining Spontaneity of Reaction Using ΔSuniv:

ΔSuniv = ΔSsys + ΔSsurr
= −199 J/K· mol + 311 J/K ·mol
ΔSuniv = 112 J/K ·mol
Because the ΔSuniv is positive, the reaction is spontaneous at 25 oC.

Gibbs Free Energy, G

Gibbs Free energy is another thermodynamic property that is used to predict whether the
reaction or process will be spontaneous or non-spontaneous.

Gibbs free energy is defined as: G = H – TS

The change in free energy (ΔG) of a system for a constant-temperature process is
ΔG = ΔH –TΔS
ΔG < 0 The reaction is spontaneous in the forward direction.
ΔG > 0 The reaction is nonspontaneous. The reaction is spontaneous in the opposite
direction.
ΔG = 0 The system is at equilibrium. There is no net change.

Summary of conditions for spontaneity and equilibrium at constant temperature and

pressure in terms of ΔG.

ΔG < 0 The reaction is spontaneous in the forward direction

ΔG > 0 The reaction is nonspontaneous. The reaction is spontaneous in the

opposite direction.

ΔG = 0 The system is at equilibrium. There is no net change.

Example 1: Calculate ΔG at 25°C for the following reaction, will this reaction be
spontaneous at this temperature? (Adapted from General Chemistry 2
Module)

CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)

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 S° J/K mol: 159.8 205.1 213.7 188.8
ΔHf kJ/mol: (-484.5)
o (-393.5) (-241.8)
ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(2) (213.7) + (2)(188.8)] – [(1)(159.8) + (2) (205.1)]
ΔS° = 235 J/K mol
ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(2) (-393.5) + (2) (-241.8)] – [(1) (-484.5) + (2) (0)]
ΔH° = - 1755 kJ
ΔG = ΔH - TΔS
= - 1755 kJ - (298K) (235 J/K) ( 1kJ/1000J)
ΔG = -1825.03 kJ
Since ΔG is negative the reaction will form the products.

Example 2: Calculate ΔG for the following reaction at 25°C. Will the reaction occur (be
spontaneous)? How do you know? (Adapted from General Chemistry 2
Module)

NH3(g) + HCl(g) → NH4Cl(s)

Also given for this reaction:

ΔH = -176.0 kJ ΔS = -284.8 J/K

We will calculate ΔG using the formula

ΔG = ΔH - TΔS

but first we need to convert units for ΔS and temperature to Kelvin:

ΔS = -284.8 J·K-1 = -0.2848 kJ/K
K = 273 + °C = 273 + 25 = 298 K

Now we can solve our equation:

ΔG = -176.0 - (298)(-0.2848)
ΔG = -176.0 - (-84.9)
ΔG = -91.1 kJ

Since ΔG < 0 the reaction will be spontaneous.

Free energy and Chemical Equilibrium: Relating ΔG° to the Equilibrium Constant
When the reactants are not in standard states (other than 1 atm pressure or 1 M),
the free energy change is related to the standard free energy change, ΔG°, by the
following equation.
ΔG = ΔG° + RT ln Q

Example 1: Consider the reaction, H2(g) + Cl2(g) → 2 HCl(g)

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 How does the value of G change when the pressures of the gases are altered
as follows at 25 C?
H2 = 0.25 atm; Cl2 = 0.45 atm; HCl = 0.30 atm
Gfo (KJ/mol) H2(g) + Cl2(g) → 2 HCl(g)
0 0 (-95.27)
G° = [2(−95.27 kJ/mol)] − [0 + 0] = −190.54 kJ/mol
(P )2 (0.30)2
QP = HCl = = 0.80
(P ) (P ) (0.25) (0.45)
H Cl
2 2
G = −190,540 J/mol + (8.314J/K·mol)(298 K) ln (0.80)
G = − 191.09 kJ/mol (the reaction becomes more spontaneous - free energy
is more negative)

Example 2: Find the value for the equilibrium constant, K, at 25 °C (298 K) for the
following reaction. The standard free energy change, ΔG°, at 25 °C equals
–13.6 kJ.

2NH3 (g) + CO2 (g) ⇆ NH2CONH2 (aq) + H2O(l)

Rearrange the equation

ΔG° = −RT ln K
to give equation
ΔG°
ln K =
− RT
Substituting numerical values into the equation,
ΔG°= 13.6 x 103 J / (8.31 J/(mol K)( 298 K)
ln K = 5.49
K = e5.49
K = 2.42×102

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 Module in General Chemistry 2
Grade 11
Fourth Quarter
Week 2

MOST ESSENTIAL LEARNING COMPETENCIES

• Explain chemical equilibrium in terms of the reaction rates of the forward and the
reverse reaction
(STEM_GC11CE-IVb-e-145)
• Calculate equilibrium constant and the pressure or concentration of reactants or
products in an equilibrium mixture (STEM_GC11CE-IVb-e-148)
• State the Le Chatelier’s principle and apply it qualitatively to describe the effect of
changes in pressure, concentration and temperature on a system at equilibrium
(STEM_GC11CE-IVb-e-149)

WHAT’S IN

Chemical equilibrium
Chemical equilibrium is the state of a reversible reaction where the rate of the
forward reaction equals the rate of the reverse reaction. In a reversible reaction, the
formation of products by the reactants occurs simultaneously with the reformation of the
reactants by the products. The two opposing processes proceed at different rates but will
reach equilibrium when the rates of the forward and backward reactions are the same
(marked by the broken line in Figure 1).

Figure 1. Changes in the rate of the forward and backward reactions in a reversible
reaction. https://www.jove.com/science-education-library/116/chemical-equilibrium

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In a state of chemical equilibrium, since the rate of product formation is equal to the rate
of the reformation of the reactants, then the concentrations of the reactants and products
remain becomes constant (Figure 2).

Figure 2. Changes in the amount of reactants and products in a reversible reaction.

https://byjus.com/chemistry/rate-of-reaction/

The Equilibrium Constant

The equilibrium constant, K, expresses the relationship between products and
reactants of a reaction at equilibrium with respect to a specific unit.

Homogeneous equilibrium is an equilibrium in which all reactants and products are in the
same phase.
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);
CO(g) + H2O(g) ⇄ CO2(g) + H2(g)

Heterogeneous equilibrium is an equilibrium in which all reactants and products are not
in the same phase.
CaCO3(s) ⇄ CaO(s) + CO2(g);
HF(aq) + H2O(l) ⇄ H3O+(aq) + F-(aq);
PbCl2(s) ⇄ Pb2+(aq) + 2 Cl-(aq)

For a reaction:
⎯
a A + bB ⎯→ c C + d D
⎯⎯

For gases:
PCc  PDd
KP =
PA a  PBb

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For solutions:
[C]c [D]d
Kc =
[A]a [B]b

The rule for heterogeneous equilibria is as follows:

1. Do not include the concentrations of pure solids and pure liquids in Kc expressions.
2. Only partial pressures for gas-phase substances or concentrations in solutions are
included in the expressions of equilibrium constants.

Write the expressions for Kp for the following reactions:

⎯
(a) NH4NO3 (s ) ⎯→ N O(g ) + 2 H O(g )
⎯⎯
( )
2 2 2
(a) K P = P N2O  PH2O

⎯
(b) Cu(s ) + Cl2 (g ) ⎯→ CuCl (s )
⎯⎯ 1
2 (b) K P =
PCl2

Example. A mixture of hydrogen and nitrogen in a reaction vessel is allowed to attain

equilibrium at 472 °C. The equilibrium mixture of gases was analyzed and found to
contain 7.38 atm H2, 2.46 atm N2 and 0.166 atm NH3. From these data, calculate the
equilibrium constant Kp for the reaction: N2(g) + 3 H2(g) 2 NH3(g).

Conversion of Kc to Kp:
To convert Kc to Kp, the following equation is used:
Kp = Kc (RT)∆n

Where:
R=0.0821 L atm/mol K or 8.31447 J/mol K
T= Temperature in Kelvin
Δngas= Moles of gas (product) - Moles of Gas (Reactant)

Example: What is the KP at 25°C for this reaction if the Kc is 4.2 × 10−2? (Adapted from
General Chemistry 2 Module)

N2(g) + 3 H2(g) ⇄ 2 NH3(g)

Δn = 2 − 4 = −2 mol
KP = (4.2 × 10−2)(0.0821)(298)−2 = 7.0 × 10−5

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Why do we omit pure solids and pure liquids in the equilibrium constant expression?
When the mass of a certain pure solid substance is doubled, its volume is also
doubled. Therefore, when the mass and volume are related, to get the concentration, a
constant value is obtained. Only reactants and products whose concentration varies
during a chemical reaction are included in the expression.

General Chemistry 2.pdf

Reaction Quotient

Reaction quotient, Q, refers to the ratio of products to reactants at any point in the reaction
(not in equilibrium state). The reaction quotient is determined the same way as in
equilibrium constant K, but is not necessarily equal to K (since it occurs in any conditions
and not in equilibrium state). It is used to predict which direction will the reaction proceed
at any given time.
If Q>K, then the reactions shifts to the left to reach equilibrium. If Q<K, then the reactions
shifts to the right to reach equilibrium. If Q=K, then the reaction is at equilibrium
Example 1: 0.035 moles of SO2, 0.500 moles of SO2Cl2, and 0.080 moles of Cl2 are
combined in an evacuated 5.00 L flask and heated to 100oC. What is Q
before the reaction begins? Which direction will the reaction proceed in
order to establish equilibrium?
SO2Cl2(g) ⇄ SO2(g) + Cl2(g) Kc = 0.078 at 100oC
[SO2][Cl2]
Qc =
[SO2Cl2]

0.500 mole SO2Cl2/5.00 L = 0.100 M SO2Cl2

0.035 mole SO2/5.00 L = 0.070 M SO2
0.080 mole Cl2/5.00 L = 0.016 M Cl2

Qc = [0.0700.100
][0.016]
= 0.011

0.078 (K) > 0.011 (Q)

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Since K >Q, the reaction will proceed in the forward direction in order to increase the
concentrations of both SO2 and Cl2 and decrease that of SO2Cl2 until Q = K.

Example 2: The Kc value for the reaction N2(g) + 3 H2(g) → 2 NH3(g) at 472°C is 0.105.
Suppose a mixture of 2.00 mol of H2, 1.00 mol of N2 and 2.00 mol of NH3 is
placed on a sealed 1.00-L container. How would we know if the reaction is
already at equilibrium?
[NH3]^2
Qc =
[N2][H2]^3

[2.00]^2
Qc =
[1.00][2.00)^3

Qc = 0.500

Since the Qc ≠ Kc, then the given mixture is not in equilibrium.

In what direction will the reaction proceed in order to attain the equilibrium?
To attain equilibrium, the quotient must decrease to 0.150. This will only happen if the
concentration of NH3 will decrease and the concentrations of N2 and H2 will increase.
Thus, the reaction must proceed in the backward direction until equilibrium is attained.

Le Châtelier's Principle

The Le Châtelier's principle states that:

when factors that influence an equilibrium are altered, the equilibrium will shift to
a new position that tends to minimize those changes.

Changes in Concentration
If additional reactant is added to a system, the equilibrium will shift to the right,
towards the products since, more reactants lead to the formation of more products. If the
concentration of the product will be reduced or decreased, the equilibrium will also shift
to the right since formation of products is needed to achieve equilibrium.
Conversely, if additional product is added to a system, the equilibrium will shift to the
reactants side (to the left) since more reactants must be produced. If reactants will be
removed from a system, equilibrium will also shift to the left.

Changes in Pressure
A change in pressure or volume will lead to greater or fewer moles so that equilibrium will
be restored. Let’s say if the pressure increases, the volume decreases, the equilibrium
will shift to the side of the reaction with fewer number of moles. Then, if the pressure
decreases. The volume increases, more moles of gas will be produced.

16
Changes in Temperature
If the reaction is endothermic, heat is being absorbed by the system and the value
of ΔH is positive. Therefore, we can consider heat as one of the reactants. Conversely,
if the reaction is exothermic, heat is released, thus, heat is a product and the value of ΔH
is negative. Increasing the temperature on an endothermic reaction will shift the
equilibrium to the right. While, decreasing the temperature on an endothermic reaction
will shift the equilibrium to the left. If the temperature is increased in an exothermic
reaction, the equilibrium will shift to the left while if the temperature is decreased, the
equilibrium will shift to the right.

Addition of an Inert Gas

An inert gas will not react with either the reactants or the products, so there will be
no change on the ratio of the product/reactant, thus, no effect on equilibrium of the
system.

Addition of a Catalyst
Catalysts do not have an effect on equilibrium of the system. They just speed up
chemical reactions and help achieve equilibrium faster.

STRESS SHIFT WHY?

Increase concentration of a Away from substance Extra concentration needs

substance to be used up
Decrease concentration of a Towards substance Need to produce more of
substance substance to make up for
what was removed
Increase pressure of system Towards fewer moles of For gas:pressure
gas increase=volume decrease
Decrease pressure of system Towards more moles of For gas:pressure
gas decrease=volume increase
Increase temperature of Away from heat/energy Extra heat/energy must be
system exothermic reaction is used up
favored
Decrease temperature of Towards heat energy More heat/energy needs to
system be produced to make up
for the loss
Add a catalyst No shift The rates of both forward
and reverse reactions are
increased by the same
amount

17
 Module in General Chemistry 2
Grade 11
Fourth Quarter
Week 3

MOST ESSENTIAL LEARNING COMPETENCIES

1. Define Bronsted acids and bases. (STEM_GC11AB-IVf-g-153)

2. Discuss the acid-base property of water. (STEM_GC11AB-IVf-g-154)
3. Calculate ph from the concentration of hydrogen ion or hydroxide ions in aqueous
solutions. (STEM_GC11AB-IVf-g-156)
4. Describe how a buffer solution maintains its ph. (STEM_GC11AB-IVf-g-160)
5. Calculate the ph of a buffer solution using the Henderson Hasselbalch equation.
(STEM_GC11AB-IVf-g-161)

WHAT’S IN

Acids and Bases Brønsted-Lowry

Arrhenius definition of acid and base is limited to aqueous (that is, water) solutions.
Although this is useful because water is a common solvent, it is limited to the relationship
between the H+ ion and the OH− ion. In 1923, new Danish chemist Johannes Nicolaus
Brønsted and English chemist Thomas Lowry independently proposed definitions for
acids and bases, ones that focus on proton transfer.
Acid: A substance that produces H3O+ ions in aqueous solution.
Base: A substance that produces OH- ions in aqueous solution.

When HCl, for example, dissolves in water, it reacts with water to give hydronium ion and
chloride ion.

With bases, the situation is slightly different:

Many bases are metal hydroxides such as NaOH, KOH, Mg(OH) 2, and Ca(OH)2.

18
These compounds are ionic solids and when they dissolve in water, their ions become
hydrated and separate:

Not all bases initially contain hydroxide ions. Some bases produce OH- by reacting
with water molecules, here shown for ammonia:

We use curved arrows to show the transfer of a proton from water to ammonia.
The first arrow shows the formation of an N-H bond, the second shows breaking of an H-
O bond.

A Brønsted-Lowry acid is any species that can donate a proton (H+) to another
molecule while base is any species that can accept a proton. In short, a Brønsted-Lowry
acid is a proton donor (PD), while a Brønsted-Lowry base is a proton acceptor (PA).
The definition is expressed in terms of an equilibrium expression.
acid + base ⇌ conjugate base + conjugate acid
With an acid, HA, the equation can be written symbolically as:
HA + B ⇌ A− + HB+ or A + B ⇌ CB + CA
• The equilibrium sign, ⇌, is used because the reaction can occur in both forward
and backward directions.
• The acid, HA, can lose a proton to become its conjugate base, A −.
• The base, B, can accept a proton to become its conjugate acid, HB +.

*Most acid-base reactions are fast so that the components of the reaction are usually in
dynamic equilibrium with each other.
Example 1
Consider the following acid–base reaction.
CH3COOH + H2O ⇌ CH3COO− + H3O+
Identify the acid (A), base (B), conjugate base (CB), and conjugate acid (CA).

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Answer/solution:

A CB
CH3COOH + H2O ⇌ CH3COO− + H3O+

B CA

*CH3COOH (acetic acid), is an acid because it donates a proton to water (H 2O) and
CH3COO− (acetate) becomes its
conjugate base.
* H2O is a base because it accepts a proton from CH3COOH and becomes its conjugate
acid, the hydronium ion, (H3O+).
• The reverse of an acid-base reaction is also an acid-base reaction, between the
conjugate acid of the base in the first reaction and the conjugate base of the acid.
In the above example, acetate is the base of the reverse reaction and hydronium
ion is the acid.

Example 2
H3O+ + CH3COO− ⇌ CH3COOH + H2O
A B CA CB
• The power of the Brønsted–Lowry theory is that, in contrast to Arrhenius theory, it
does not require an acid to dissociate.

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The Amphoteric Nature of Water
A substance which can act as either an acid or a base is described as amphoteric.
• Water is amphoteric because it can act as an acid or as a base. In the image shown
at the right one molecule of H2O acts as a base and gains H+ to become H3O+while
the other acts as an acid and loses H+ to become OH−.

or
For pure water at 25 oC

K w = [H3O+ ][OH− ]

K w = (1 x 10−7 ) x (1 x 10−7 ) = 1 x 10−14

Relative amounts determine if the solution is acid, base, or neutral.
When [H3O+] = [OH−], the solution is neutral.
When [H3O+] > [OH−], the solution is acidic.
When [H3O+] < [OH−], the solution is basic.

pH and Buffer Solution

• A basic solution will have a pH above 7.0, while an acidic solution will have a pH
below 7.0.
• Buffers are solutions that contain a weak acid and its conjugate base; as such,
they can absorb excess H+ ions or OH– ions, thereby maintaining an overall steady
pH in the solution.
• pH (power or potential of Hydrogen) is equal to the negative logarithm of the
concentration of H+ ions in solution: pH = – log[H+].
• For hydroxides: pOH = -log [OH-]

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 Therefore: pH + pOH = 14
• To know the molar concentration [H+] = 10-pH
[OH-] = 10-pOH

Example 1:
What is the pH of the solution if the [H+] or [H3O+] concentration is 2.5 x 104 M?
Solution: pH = -log [H+]
= - log 2.5 x 104M
= 3.6
Example 2:
The pOH of the solution is 4.5. Calculate the pH and determine if acidic or basic.
Solution: pH + pOH = 14
pH = 14 - pOH
= 14 - 4.5
= 9.5 basic

Strong Acids and Strong Bases

The stronger the acid, the more readily it donates H+. For example, hydrochloric acid
(HCl) is highly acidic and completely dissociates into hydrogen and chloride ions, whereas
the acids in tomato juice or vinegar do not completely dissociate and are considered weak
acids; conversely, strong bases readily donate OH– and/or react with hydrogen ions.
Sodium hydroxide (NaOH) and many household cleaners are highly basic and give up
OH– rapidly when placed in water; the OH– ions react with H+ in solution, creating new
water molecules and lowering the amount of free H+ in the system, thereby raising the
overall pH. An example of a weak basic solution is seawater, which has a pH near 8.0,
close enough to neutral that well-adapted marine organisms thrive in this alkaline
environment.

Buffers

How can organisms whose bodies require a near-neutral pH ingest acidic and basic
substances (a human drinking orange juice, for example) and survive? Buffers are the
key. Buffers usually consist of a weak acid and its conjugate base; this enables them to
readily absorb excess H+ or OH–, keeping the system’s pH within a narrow range.

Maintaining a constant blood pH is critical to a person’s well-being. The buffer that

maintains the pH of human blood involves carbonic acid (H2CO3), bicarbonate ion

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(HCO3–), and carbon dioxide (CO2). When bicarbonate ions combine with free hydrogen
ions and become carbonic acid, hydrogen ions are removed, moderating pH changes.
Similarly, excess carbonic acid can be converted into carbon dioxide gas and exhaled
through the lungs; this prevents too many free hydrogen ions from building up in the blood
and dangerously reducing its pH; likewise, if too much OH– is introduced into the system,
carbonic acid will combine with it to create bicarbonate, lowering the pH. Without this
buffer system, the body’s pH would fluctuate enough to jeopardize survival.

Buffers in the body. This diagram shows the body’s buffering of blood pH levels: the
blue arrows show the process of raising pH as more CO2 is made; the purple arrows
indicate the reverse process, lowering pH as more bicarbonate is created.

Antacids, which combat excess stomach acid, are another example of buffers. Many over-
the-counter medications work similarly to blood buffers, often with at least one ion (usually
carbonate) capable of absorbing hydrogen and moderating pH, bringing relief to those
that suffer “heartburn” from stomach acid after eating.

Henderson-Hasselbalch equation
The Henderson–Hasselbalch equation was developed independently by the
American biological chemist L. J. Henderson and the Swedish physiologist K. A.
Hasselbalch, for relating the pH to the bicarbonate buffer system of the blood. This
equation relates pH, pKa, and molar concentration.

[base] Other Related equations: pKa = -log Ka

pH = pKa + log ––––– pKb = -log Kb

pOH = pKb + log ([HB+]/[ B ]
[acid]
pKa + pKb =14

Note: pKa = refers to acid dissociation constants (it can be found in Table of K a)
Steps in Solving Problems Related to Buffer and Henderson-Hasselbalch
equation
1. Identify the weak acid and conjugate base.
2. Derive the equation if necessary.
3. Plug in the values into the equation.

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Example 1:
Calculate the pH of a buffer solution made from 0.20 M HC2H3O2 and 0.50 M C2H3O2-
that has an acid dissociation constant for HC2H3O2 of 1.8 x 10-5.
Solution:
pH = pKa + log ([A-]/[HA])
pH = pKa + log ([C2H3O2-] / [HC2H3O2])
= -log (1.8 x 10-5) + log (0.50 M / 0.20 M)
= -log (1.8 x 10-5) + log (2.5)
= 4.7 + 0.40
= 5.1

Example 2:
How much sodium formate (HCOONa, 68.0069 g/mol) do you need to add to 400. mL of
1.00 M formic acid for a pH 3.500 buffer. Ka = 1.77 x 10-4?

pH = pKa + log [base/acid]

3.500 = 3.752 + log (x / 1) <--- that 1 comes from the 1.00 M formic acid

log x = −0.252

x = 0.560 M (this is the molarity of the formate that is required)

MV = g/molar mass

(0.560 mol/L) (0.400 L) = x / 68.0069 g/mol

x = 15.2 g

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