12

GENERAL CHEMISTRY 2
(STEM)
QUARTER 4 – MODULE 1 & 2

Spontaneous Change, Entropy, and Free Energy

 What’s New

Before you proceed, you should be familiar with the definition of the following words that you will
encounter as you go through the lesson:
Endothermic process
Process that absorbs heat from the surroundings

Exothermic process
Process that gives off heat to the surroundings

Thermodynamics
A scientific discipline that deals with the interconversion of heat and other forms of energy

Enthalpy, H
A thermodynamic quantity used to describe heat changes taking place at constant pressure

Enthalpy of reaction, ΔHrxn

The difference between the enthalpies of the products and the enthalpies of reactants

Spontaneous process
A physical or chemical change that occurs by itself. A process that takes place without energy from an
external source

Entropy, S
A thermodynamic quantity that is a measure of how spread out or dispersed the energy of a system is
among the different possible ways that system can contain energy

Standard entropy, S°
The absolute entropy of a substance at 1 atm and 25 °C

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Gibbs Free Energy, G
Energy available to do useful work. Used to express the spontaneity of a reaction more directly

Standard Free Energy, ΔGrxn°

The free energy change for reaction when it occurs under standard state conditions, when reactants in their standard
states are converted into products in their standard states

In your previous lesson, it was discussed that the first law of thermodynamics states that energy
can be converted from one form to another, but it cannot be created or destroyed. One measure
of these changes is the amount of heat given off or absorbed by a system during a constant-
pressure process, which chemists define as a change in enthalpy (ΔH).
A. SPONTANEOUS PROCESSES

What is a spontaneous process and its examples?

A spontaneous process is a physical or chemical change that occurs by

itself. These processes occur without requiring an outside force and continue until
equilibrium is reached.

Examples:

• A lump of sugar spontaneously dissolves in a cup of coffee, but dissolved sugar

does not spontaneously reappear in its original form.
• Water freezes spontaneously below 0°C, and ice melts spontaneously above 0°C (at
1 atm).
• Heat flows from a hotter object to a colder one, but the reverse never happens
spontaneously.
• A piece of sodium metal reacts violently with water to form sodium hydroxide and
hydrogen gas. However, hydrogen gas does not react with sodium hydroxide to
form water and sodium.
• Iron exposed to water and oxygen forms rust, but rust does not spontaneously
change back to iron.

These examples show that processes that occur spontaneously in one direction
cannot, under the same conditions, also take place spontaneously in the opposite
direction.

How does spontaneity apply to chemical reactions?

In a chemical reaction, ΔHreaction = Hproducts - Hreactants. If it is exothermic,

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then ΔHreaction = (-). To get a negative ΔHreaction , the Hproducts must be lower than the Hreactants.

A spontaneous process is one that takes place without energy from an

external source. For a chemical reaction to be spontaneous, it should proceed as
written (from left to right), without an input of energy.
In most cases, exothermicity (example 1 and 2) favors the spontaneity of a
reaction but does not guarantee it. Just as it is possible for an endothermic reaction to
be spontaneous (example 3 and 4), it is possible for an exothermic reaction to be
nonspontaneous.

Example 1: Exothermic Reaction

Combustion of methane:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ΔH° = -890.4 kJ/mol

Example 2: Exothermic Reaction

Acid-base neutralization reaction:

H+(aq)+ OH-(aq)  H2O(l) ΔH° = -56.2 kJ/mol

Example 3: Endothermic Reaction

H2O(s)  H2O(l) ΔH° = 6.01 kJ/mol

Example 4: Endothermic Reaction

H O
NH4NO3(s) 2 NH4+ (aq) + NO3- (aq) ΔH° = 25 kJ/mol

We cannot decide whether a chemical reaction will occur spontaneously solely

on the basis of energy changes in the system. To make this kind of prediction, we
need another thermodynamic quantity, which turns out to be entropy.

B. Entropy

What is entropy? How does it relate to spontaneity of a process?

Entropy, S, is a thermodynamic quantity that is a measure of how spread out or

dispersed the energy of a system is among the different possible ways that system can
contain energy. It is a quantity that is generally used to describe the course of a
process, that is, whether it is a spontaneous process and has a probability of occurring
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in a defined direction, or a non-spontaneous process and will not proceed in the
defined direction, but in the reverse direction. The SI unit of entropy is joules per Kelvin
(J/K) and, like enthalpy, is a state function.

How do entropy changes occur?

Most processes are accompanied by entropy change. The following are

processes that lead to an increase in entropy of the system:

Table 1.1: Processes that lead to an increase in • Entropy change examples:

entropy of the system ➡ Molecules of gas at high
pressure always spread to lower
Process Order Disorder pressure regions.
Melting Solid Liquid
➡ Gas in balloon spreads out into
Vaporization Liquid Vapor room and deflates but never see
Dissolving Solute Solution balloon spontaneous fill with air.
Heating System at T1 System at T2 (T2 > T1)
➡ Heat always goes from high
temperature into cooler regions.

➡ Hot coffee in a room gets

cooler and the heat spreads out
into the room, but never sees a
cold cup of coffee spontaneously
warm up.

The spreading out of more concentrated molecules and the spreading out of more
concentrated energy are changes from more order to more random. The changes that
occur are the ones that lead to an increasing randomness of the universe. Entropy is
sometimes referred as the measure of randomness and disorder.

heat (direction of heat flow)

Figure 1.1. The increase of randomness and disorder of particles from solid to vapor.

At high enough temperature, the spontaneous change is from Solid -Liquid-

Gas; gas is more random than liquid and liquid is more random than solid. There is an
increase in entropy (S) of the system by going from solid to liquid to gas.

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 C. Entropy and the Second Law of Thermodynamics

The second law of thermodynamics explains why chemical processes tend to

favor one direction. This law states that the entropy of the universe increases in a
spontaneous process and remains unchanged in an equilibrium process. Meanwhile,
the third law states that the entropy of a perfect crystalline substance is zero at the
absolute zero of temperature (T = 0K= -273.15 oC). Because the universe is made up

of the system and the surroundings, the entropy change in the universe (ΔSuniv) for
any process is the sum of the entropy changes in the system (ΔSsys) and in the
surroundings (ΔSsur).

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

How is entropy change determined? What data are needed for the calculation?

Suppose that the system is represented by the following reaction:

aA + bB  cC + dD

As in the case for the enthalpy of a reaction, the standard entropy of reaction
ΔS°rxn is given by the difference in standard entropies between the products and the
reactants.

ΔS° = ΣnS°(products) - ΣmS°(reactants)

Where m and n are the stoichiometric coefficients in the reaction.

ΔS° rxn = [cSo (C) + d So (D)] ‒ [aSo (A) + bSo (B)]

The standard entropy values of compounds have been measured in J/K mol. To
calculate the ΔS° rxn (which is the ΔSsys), the values may be found in the
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 Thermodynamic Data Table. Thermodynamic tables (table 1) have absolute entropy
of substances at 25°C and 1atm.

• For convenience, ΔS° will be used instead of ΔS° rxn in the proceeding discussion.
Remember, the greater the value of ΔS then the greater is the increase in the
randomness of the system.

Table 1.2: Standard Molar Entropies So(J/mol.K) of

Selected Substances at 298K

H2(g) 130.6
N2(g) 191.5
O2(g) 205.0
H2O(g) 188.8
NH3(g) 192.5
CH3OH(g) 237.6
C6H6(g) 269.2
H2O(l) 69.9
CH3OH(l) 126.8
C6H6(l) 172.8
Li(s) 29.1
Na(s) 51.4
K(s) 64.7
Fe(s) 27.23
FeCl3(s) 142.3
NaCl(s) 72.3

Sample Problem C1:

From the standard entropy values in the Thermodynamic Data table, calculate ΔS°
for the following reaction.

H2(g) + I2(s)  2HI(g)

Step 1. Write the standard entropy of each formula.

S°(J/K·mol): H2(g) 130.6

I2(s) 116.7
HI(g) 206.3

Step 2: Using the equation for the standard entropy of reaction

ΔS° = ΣnS°(products) - ΣmS°(reactants)

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 = [(2) So HI] – [(1) So H2 + (1) So I2

Step 3: Substitute the entropy values

= [ (2) (206.3) ] – [ (1) (130.6) + (1) (116.7) ]

= [ 412.6 ] – [ 247.3 ]

ΔS° = +165.3 J/K

What general rules apply to predicting whether an entropy change is negative or

positive?
General rules for predicting entropy change of the system:
1. If the reaction produces more gas molecules than it consumes, ΔS° is positive.
2. If the total number of gas molecules diminishes, ΔS° is negative.
3. If there is no net change in the total number of gas molecules, ΔS° may be
positive or negative, but will be relatively small numerically.

Sample Problem C2:

Predict whether the entropy change of the system in each of the following is positive
or negative.
1. O2(g)  2O(g)

2. N2(g, 10 atm)  N2(g, 1atm)

3. 6CO2(g) + 6H2O(g)  C6H12O6(g) + 6O2(g)

4. 2 H2(g) + O2(g)  2 H2O(l)

5. NH4Cl(s)  NH3(g) + HCl(g)

Expected answer:

1. Positive. Increase in number of gas molecules

2. Positive. Decrease in pressure of the system will increase entropy
3. Negative. Decrease in number of gas particles
4. Negative. Net decrease in number of molecules and gases are converted to solids
5. Positive. A solid is converted to two gaseous products.

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Sample Problem C3:

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 25oC 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

Expected answers:

1. -169.2 J/K·mol
2. -22.2 J/K·mol
3. +198.8 J/K·mol

D. Gibbs Free Energy, G

What is Gibbs free energy? How does it relate to the spontaneity of a
reaction?

Another thermodynamic function is used in order to express the spontaneity of

a reaction more directly. This is called Gibbs free energy, G. The use of G predicts
changes that are focused on the system.

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

ΔG = ΔH- TΔS

• All the quantities in the equation pertain to the system; the temperature T is the
temperature of the system.
• G has units of energy; both H and TS are in energy units.
• H, S and G are all state functions.

If the entropy of the universe increases then the ΔG of the system will decrease. The
direction of spontaneous change is negative ΔG for system. The ΔG tells us if a change can
occur for a chemical reaction.

If ΔSuniv is (+) for universe then ΔG for system is ( - ). The ΔG for the system is

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 a convenient way to predict a change.

How can the spontaneity of a reaction be predicted using Gibbs free

energy change, ΔG?

The change in free energy (ΔG) of a system for a constant-temperature process is

ΔG = ΔH –TΔS

In this context, free energy is the energy available to do work. If a particular reaction
is accompanied by a release of usable energy (ΔG is negative), the reaction is spontaneous.
Unless stated otherwise, the ΔH, ΔS and ΔG refer to the system at 25 oC. Most
of our calculations are for values of ΔG at 25oC (298 K).

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.

Table 1.3: The effect of ΔH, ΔG and T on spontaneity

How is Gibbs free energy change determined when ΔH and ΔS are available?

ΔG = ΔH –TΔS

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Sample Problem D1:
The old camera flash bulb used Mg metal sealed in a bulb with oxygen. The reaction
is:
Mg + ½ O2 
MgO
S° J/K mol: 32.7 205.0 26.9
ΔHfo kJ/mol: 0 0 -601.2

Calculating the ΔS°

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

= [(1) So MgO] – [(1) So Mg + (½) So O2]
= [(1) (26.9)] – [(1)(32.7) + (½) (205.0)]

ΔS° = -108.3 J/K mol

Calculating the ΔH°

ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(1) ΔHfo MgO] – [(1) ΔHfo Mg + (½) ΔHfo O2]
= [(1) (-601.2)] – [(1) (0) + (½) (0)]

ΔH° = -601.2kJ

Calculating the ΔG

ΔG = ΔH - TΔS

= 601.2kJ – [(298K) (-108.3J/K) ( 1kJ/1000J)]

= -601.2 + 32.3kJ

ΔG = -568.9kJ

Since ΔG is negative the reaction will form MgO. Looking up ΔG f (MgO) = -569 kJ based
on ΔG = [ΔGf (MgO) ] – [ΔGf (Mg) + ½ ΔGf (O2)] this reaction occurs rapidly once initiated.

Sample Problem D2:

Ozone (O3) in the atmosphere can react with nitric oxide (NO): O3(g)
+ NO(g)  NO2(g) + O2(g)

Calculate the G for this reaction at 25oC.

(H = -199 kJ/mol, S = -4.1 J/K·mol)

Expected answer: -198 kJ/mo

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Factors affecting the sign of ΔG

In order to predict the sign of ΔG according to the equation: ΔG = ΔH - TΔS, we

need to know both ΔH and ΔS. Temperature may also influence the direction of the
spontaneous reaction. The four possible combinations are shown below.

ΔH TΔS ΔG Effects
‒ + ‒ Reaction proceeds spontaneously at
all temperatures
Example: 2H2O2(aq)  2 H2O(l) + O2(g)
+ ‒ + Reaction is spontaneous in the reverse
direction at all temperatures
Example: 3O 2(g) 
2O3(g)
+ + ? Reaction proceeds spontaneously at high
temperatures. At low temperatures, the
reverse reaction becomes spontaneous.
Example: 2HgO(s)  2Hg(l) + H2O(g)
‒ ‒ ? Reaction proceeds spontaneously at low
temperatures. At high temperatures, the
reverse reaction becomes spontaneous.
Example: NH3(g) + HCl(g)  NH4Cl(s)

Sample Problem Application

Should you invest in an engine that is said to burn air at room temperature? You are
told that a special chamber allows O2 to combine with N2 to form NO2 (nitrogen
dioxide) using reaction
½ N2(g) + O2(g)  NO2(g)

Evaluate using thermodynamics

½ N2(g) + O2(g)  NO2(g)
S° J/K mol: 191.5 205.0 240.5
ΔHfo kJ/mol: 0 0 34

Calculate enthalpy change

ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(1 ) ΔHfo NO2] – [(½)ΔHfo N2 +(1) ΔHfo O2]
= [(1)(+34)] – [((½) (0) + (1)(0)]

ΔH° = +34 kJ

No heat given off only taken in.

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Calculate entropy change
ΔS° = ΣnS° (products) − ΣmS° (reactants)
= [(1 ) So NO2] – [(½) So N2 +(1) So O2]
= [(1) (240.5) ] – [(½) (191.5) + (1) (205.0)]
= 240.5 - 300.8

ΔS° = -60.3 J/K mol

Calculate Gibbs Free Energy change from above

ΔG = ΔH –TΔS

= +34kJ – (298K) (-60.3J/molK) (1kJ/1000J)

= 34 kJ + 18.0 kJ

ΔG = +52 kJ

* The reaction will NOT occur and NO heat is given off. Neither ΔH which is (+) or ΔS
which is (–) favors reaction.

Lesson
Chemical Equilibrium and
2 Le Châtelier’s Principle

The key to understanding equilibrium is entropy and the second law of

thermodynamics. A system that is isolated from all other influences may go through a
variety of spontaneous changes, some of which will increase its entropy. The entropy
cannot be reduced once it has increased. As a result, an isolated system enters a state
where the entropy is at its maximum. This is a state of equilibrium. The entropy of the
system cannot increase (because it is already at a maximum) or decrease (because it
is already at a minimum) in equilibrium (because that would violate the second law of
thermodynamics). The only modifications that are permitted are those that keep the
entropy constant.

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1.1 The Concept of Equilibrium

Many chemical reactions do not proceed to just one direction or proceed

essentially to completion. These are called reversible reactions.
In reversible reactions, the reactants are not completely converted into products
and some of the products may be converted back into reactants.

Unlike in irreversible reactions where a single headed arrow is used ( ),

reversible reactions use a double
headed arrow () to indicate that the forward and backward reactions are occurring
simultaneously. In general terms, a reversible reaction may be represented as follows:

aA + bB  cC + dD

where the lower-case letters represent the stoichiometric coefficients of the reactants
and products.

What is chemical equilibrium?

To describe the state of equilibrium, consider Figure 1.1. The figure shows a
time-lapsed photograph of the traffic entering and leaving the City of San Francisco
in California, USA.

Figure 2.1 The Golden Gate Bridge. (Image obtained from https://upload.wikimedia.org/wikipedia/commons/thumb/d/da/
Golden_Gate_Bridge_at_Night_Long_Exposure_7105222661.jpg/800pxGolden_Gate_Bridge_at_Night_Long_Expos
ure_7105222661.jpg

Assuming the rate (say number of cars per hour) at which cars enter the city is
the same as the rate at which the cars leave the city, then the two opposing processes
are in balance. This also means that there is a constant number of cars inside the city.

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A state of balance is also referred to as a state of equilibrium. In a reversible reaction,
when the reactants start to form the products, the products would then start to reform
the reactants. The two opposing processes happen at different rates but a certain point
in the reaction will be reached where the rates of the forward and backward reactions

are the same (marked by the broken line in Figure 2.2). This is the state of chemical
equilibrium.

Figure 2.2. Changes in the rate of the forward and backward reactions in a
reversible reaction.

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 constant (Figure 2.3).

Figure 2.3. Changes in the amount of reactants and products in a reversible

reaction.

The state of chemical equilibrium is a highly dynamic state. This means that
though there are no change in the composition of the reaction mixture and no visible
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changes taking place, the particles are continuously reacting. Also, a system at
chemical equilibrium can be easily disturbed by changes in the reaction
conditions.

1.2 Equilibrium Constant Expression

The relationship between the concentrations of the reactants and products may be
expressed using the law of mass action expression/equilibrium constant expression.
For the general equilibrium reaction:

aA + bB  cC + dD

the equilibrium constant expression is written as

[C]c[D]d
Keq =
[A]a[B]b

where the [ ] is the concentration expressed in molarity and Keq is the equilibrium
constant. If molar concentrations are used, Keq may also be referred to as Kc. The
law of mass action is basically the ratio of the concentrations of the products raised to
their respective stoichiometric coefficients to that of the reactants

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For the reaction:

N2O4(g) 2NO2(g)

the equilibrium constant expression is written as

[NO2]2
Keq =
[N2O4]

Equilibrium constant expression of some balanced chemical equations:

1. 2O3(g) 3O2(g) [O2]3

Keq =
[O3]2

2. 2NO(g) + Cl2(g) 2NOCl(g)

[NOCl]2
Keq = [NO]2[Cl2]

3. HF(aq) + C2O42–(aq) 2 F–(aq) + H2C2O4(aq)

[F–]2[H2C2O4]
Keq = [HF][C2O42–]

Equilibrium constants for homogeneous gaseous equilibria may also be

expressed in terms of partial pressures. The expression is written in much the same
way as described, only that the partial pressure is raised to the coefficient instead of
the molar concentration.
Example:

1. 2O3(g) 3O2(g)

[PO2]3
Kp =
[PO3]2

2. 2NO(g) + Cl2(g) 2NOCl(g)

[PNOCl]2
Keq = [PNO]2[PCl2]
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For equilibrium reactions where the reactants and products are in different phases
(heterogeneous equilibria), pure solids and pure liquids are excluded in writing equilibrium
constant expressions. For example, consider the reaction:

PbCl2(s) Pb2+(aq) + 2Cl–(aq)

The equilibrium constant expression for the reaction is:

Keq = [Pb2+][Cl-]2

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 is 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.

Example:

Balanced Chemical Equation Equilibrium Constant Expression

CO2(g) + H2(g) CO(g) + H2O(l)

[CO]
Keq =
[CO2][H2]

SnO2(s) + 2CO(g) Sn(s) + 2CO2(g)

[CO2]2
Keq =
[CO]2

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 1.3 The Equilibrium Constant, Keq

The equilibrium constant, Keq, is the numerical value that is obtained when
equilibrium concentrations are substituted to the equilibrium constant expression. The
value of Keq may vary from very large to very small values. This value provides an idea
of the relative concentrations of the reactants and products in an equilibrium mixture.

Consider the reaction for the production of phosgene (COCl 2), a toxic gas used
in the manufacture of certain polymers and insecticides, at 100°C:

CO(g) + Cl2(g) COCl2(g)

[CoCl2]
Keq = = 4.56 x 109
[CO][Cl2]

Question: If a certain fraction equates to a very large value, then which has a larger
value between the numerator and the denominator?

Answer: The numerator should have the larger value.

The large value of 4.56 × 109 suggests that the concentration of COCl2 must be very
large as compared to the individual concentrations of CO and Cl 2. The value
suggests that at equilibrium, the reactions mixture contains more of the product
COCl2 than the reactants CO and Cl2. This is experimentally verified. In other words,
the equilibrium lies to the right or towards the product side based from the
chemical equation given.

Question: Gaseous hydrogen iodide is placed in a closed container at 425°C, where

it partially decomposes to hydrogen and iodine: 2 HI(g) H2(g) + I2(g) . At
equilibrium, it is found that [HI] = 3.53 × 10 M, [H2] = 4.79 × 10–4 M and [I2] =4.79 ×
–3

10–4 M. What is the value of Keq at this temperature?

Answer:

[H2][I2] (4.79 x 10-4)(4.79 x 10-4)

Keq = = =0.0184
[HI]2 (3.53 x 10-3)2

In the second example, the value of Keq is small (< 1). For this to happen, the
value of the denominator must be larger compared to the numerator. In the case of
the given reaction, the equilibrium concentration of HI is higher than the equilibrium
concentrations of the decomposition products. This means that the equilibrium lies
on the left or on the reactant side.

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In general,

If K > 1 (large K value), the equilibrium lies to the right and the products predominate
in the equilibrium mixture.

If K < 1 (small K value), the equilibrium lies to the left and the reactants predominate
in the equilibrium mixture

NOTE: SAMPLE PROBLEMS INVOLVING EQUILIBRIUM CAN BE FOUND IN APPENDIX A.

2.1 Le Châtelier’s Principle

There is a general rule that helps us to predict the direction in which an equilibrium
reaction will move when a change in concentration, pressure, volume, or temperature occurs.
The rule, known as Le Châtelier’s principle, states that if an external stress is applied to a
system at equilibrium, the system adjusts in such a way that the stress is partially offset as the
system reaches a new equilibrium position. The word “stress” here means a change in
concentration, pressure, volume, or temperature that removes the system from the
equilibrium state. We will use Le Châtelier’s principle to assess the effects of such changes.

2.2 Changes in Concentration

Iron(III) thiocyanate [Fe(SCN)3] dissolves readily in water to give a red solution.

The red color is due to the presence of hydrated FeSCN2+ ion. The equilibrium
between undissociated FeSCN2+ and the Fe3+ and SCN- ions is given by

FeSCN2+ (aq) Fe3+ (aq) + SCN- (aq)

red pale yellow colorless

What happens if we add some sodium thiocyanate (NaSCN) to this solution? In this
case, the stress applied to the equilibrium system is an increase in the concentration
of SCN- (from the dissociation of NaSCN). To offset this stress, some Fe 3+ ions react
with the added SCN- ions, and the equilibrium shifts from right to left:

FeSCN2+ (aq) Fe3+ (aq) + SCN- (aq)

Consequently, the red color of the solution deepens (Figure 1). Similarly, if we added
iron(III) nitrate [Fe(NO3)3] to the original solution, the red color would also deepen
because the additional Fe3+ ions [from Fe(NO3)3] would shift the equilibrium from right
to left.
Now suppose we add some oxalic acid (H2C2O4) to the original solution. Oxalic
acid ionizes in water to form the oxalate ion, C2O4 2+, which binds strongly to the Fe3+
ions. The formation of the stable yellow ion Fe(C2O4)33+ removes free Fe3+ ions in

solution. Consequently, more FeSCN2+ units dissociate and the equilibrium shifts from
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left to right:

FeSCN2+ (aq) Fe3+ (aq) + SCN- (aq)

The red solution will turn yellow due to the formation of Fe(C2O4)3 3+ ions.

Figure 2.4. Effect of

concentration change on the
position of equilibrium. (a) An
aqueous Fe(SCN)3 solution. The color of
the solution is due to both the red
FeSCN2+ and the yellow Fe3+ ions. (b)
After the addition ofsome NaSCN to the
solution in (a), the equilibrium shifts to
the left. (c) After the addition of some
Fe(NO3)3 to the solution in (a), the
equilibrium shifts to the left.

(d) After the addition of some H2C2O4 to

the solution in (a), the equilibrium shifts
to the right. The yellow color is due to
the Fe(C2O4)3

”This experiment demonstrates that all reactants and products are present in the
reacting system at equilibrium. Second, increasing the concentrations of the products
(Fe3+ or SCN-) shifts the equilibrium to the left, and decreasing the concentration of the
product Fe3+ shifts the equilibrium to the right. These results are just as predicted by
Le Châtelier’s principle (Chang).”

2.3 Changes in Volume and Pressure

Changes in pressure ordinarily do not affect the concentrations of reacting species

in condensed phases (say, in an aqueous solution) because liquids and solids are
virtually incompressible. On the other hand, concentrations of gases are greatly
affected by changes in pressure.

Consider the following equilibrium systems:

(a) 2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)

(b) PCl5(g) PCl3(g) + Cl2(g)
(c) H2(g) + CO2(g) H2O(g) + CO(g)

Predict the direction of the net reaction in each case as a result of increasing the
pressure (decreasing the volume) on the system at constant temperature.

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Strategy

A change in pressure can affect only the volume of a gas, but not that of a solid because solids
(and liquids) are much less compressible. The stress applied is an increase in pressure.
According to Le Châtelier’s principle, the system will adjust to partially offset this stress. In other
words, the system will adjust to decrease the pressure. This can be achieved by shifting to the
side of the equation that has fewer moles of gas.

Solution

(a) Consider only the gaseous molecules. In the balanced equation, there are
3 moles of gaseous reactants and 2 moles of gaseous products. Therefore, the net
reaction will shift toward the products (to the right) when the pressure is increased.

(b) The number of moles of products is 2 and that of reactants is 1; therefore, the net
reaction will shift to the left, toward the reactant.

(c) The number of moles of products is equal to the number of moles of reactants, so a
change in pressure has no effect on the equilibrium.

2.4 Changes in Temperature

A change in concentration, pressure, or volume may alter the equilibrium position,

that is, the relative amounts of reactants and products, but it does not change the
value of the equilibrium constant. Only a change in temperature can alter the
equilibrium constant. To see why, let us consider the reaction

N2O4(g) 2NO2(g)

The forward reaction is endothermic (absorbs heat, ΔH° > 0):

heat + N2O4(g)  2NO 2(g) ΔH° = 58.0 kJ/mol

so the reverse reaction is exothermic (releases heat, ΔH° < 0):

2NO2(g) N2O4(g) + heat ΔH° = -58.0 kJ/mol

At equilibrium at a certain temperature, the heat effect is zero because there is no

net reaction. If we treat heat as though it were a chemical reagent, then a rise in
temperature “adds” heat to the system and a drop in temperature “removes” heat
from the system. As with a change in any other parameter (concentration, pressure,
or volume), the system shifts to reduce the effect of the change. Therefore, a
temperature increase favors the endothermic direction of the reaction (from left to
right of the equilibrium equation), which decreases [N2O4] and increases [NO2]. A
temperature decrease favors the exothermic direction of the reaction (from right to
left of the equilibrium equation), which decreases
[NO2] and increases [N2O4].

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 2.5 The Effect of a Catalyst

We know that a catalyst enhances the rate of a reaction by lowering the reaction’s
activation energy. However, a catalyst lowers the activation energy of the forward
reaction and the reverse reaction to the same extent. We can therefore conclude that
the presence of a catalyst does not alter the equilibrium constant, nor does it shift the
position of an equilibrium system. Adding a catalyst to a reaction mixture that is not at
equilibrium will simply cause the mixture to reach equilibrium faster. The same
equilibrium mixture could be obtained without the catalyst, but we might have to wait
much longer for it to happen.

Applying Le Châtelier’s principle

What effect do the following changes have on the position of equilibrium for this
reversible reaction? How must the reaction shift to relieve the “stress” caused by the
change?

PCl5(g) + heat PCl3(g) + Cl2(g)

a. addition of Cl2
b. increase in pressure
c. removal of heat
d. removal of PCl3 as it is formed
e. addition of a catalyst

Solution:
a. The addition of Cl2 shifts the equilibrium to the left, forming more PCl5.
b. There are 2 moles of gaseous products and 1 mole of gaseous reactant. The increase
in pressure is relieved if the equilibrium shifts to the left. A decrease in the number
of moles of gaseous substance gives a decrease in pressure.
c. Removal of heat causes a shift to the left because the reverse reaction
produces heat.
d. Removal of PCl3 causes a shift to the right to produce more PCl5.
e. No change

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Grade GENERAL CHEMISTRY 2

12 Quarter 4 - Module 1&2

Module Title: Spontaneous Change, Entropy, and Free Energy
3
Name: _______________________________________________________
Grade & Section: ________________________Strand: ________________

A. Multiple Choice
Directions: Write the letter of the best answer on your answer sheet.

1. In which of the following physical states does a given substance have the
highest entropy?
a. solid
b. gas
c. liquid
d. The entropy is the same because the same substance is involved.

2. Which of the following describes an endergonic reaction?

a. must be endothermic
b. is nonspontaneous
c. must correspond to a decrease in entropy
d. is spontaneous

3. What are the two factors that determine whether a reaction is spontaneous or
nonspontaneous?
a. entropy and disorder
b. entropy and enthalpy change
c. electron configuration and change
d. energy and the heat of reaction

4. In which of these systems is the entropy decreasing?

a. air escaping from a tire
b. snow melting
c. salt dissolving in water
d. gas condensing to a liquid

5. Which of the following refers to all spontaneous processes?

a. are exothermic
b. are endothermic
c. involve an increase in entropy
d. release free energy

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6. What is the expression for Keq for this reaction?

2H20(g)  2H2(g) + 02(g)

[2H20] [2H2] x [02]

a. Keq = c. Keq =
[H2] x [02] 2[H20]

[H2]2 x [02] [H20]2

b. Keq = d. Keq =
[H20]2 [H2]2 x [02]

7. In an equilibrium reaction with a Keq of 1 x 108, which of the following is true?

a. reactants are favored c. products are favored
b. reaction is nonspontaneous d. reaction is exothermic

8. What is the effect of adding more C02 to the following equilibrium reaction?
C02 + H20 H2C03

a. More H2C03 is produced.

b. More H20 is produced.
c. The equilibrium is pushed in the direction of reactants.
d. Nothing

9. Doing which of the following generally increases the entropy of a substance?

a. freezing it c. condensing it
b. dissolving it in water d. all of the above

10. The Keq of a reaction is 4 x 10-7. At equilibrium:

a. the reactants are favored.
b. the products are favored.
c. the reactants and products are present in equal amounts.
d. the rate of the reverse reaction is much greater than the rate of the
forward reaction.

11. Two opposing reactions (A + B C + D) occurring simultaneously at the

same rate is an example of:
a. reversibility c. neither a nor b
b. chemical equilibrium d. both a and b

12. Exergonic reactions:

a. are nonspontaneous.
b. release free energy.
c. do not produce energy that can be used to do useful work.
d. all of the above

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13. A reaction is most likely to be spontaneous when during the course of a
reaction:
a. the energy content and the entropy both increase.
b. the energy content increases and the entropy decreases.
c. the energy content decreases and the entropy increases.
d. the energy content and the entropy both decrease.

14. The amount of disorder in a system is measured by its:

a. activation energy c. equilibrium position
b. entropy d. Keq

15. On a cold day water vapor condenses to form frost. This represents an:
a. entropy increase and enthalpy increase
b. entropy increase and enthalpy decrease
c. entropy decrease and enthalpy increase
d. entropy decrease and enthalpy decrease

B. Matching Type

Directions: Match each term in Column B with the correct description in Column A.
Write the letter of the correct term on your answer sheet.

Critical Thinking Challenge

Directions: Answer the question below.

1. The rusting of iron is spontaneous and is accompanied by a decrease in the

entropy of the system (the iron and oxygen). What can we conclude about the
entropy change of the surroundings?

2. What is Le Châtelier's principle? Use it to explain why carbonated drinks go

flat when their containers are left open.

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