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Equilibrium in Chemistry Explained

The document covers the concepts of static and dynamic equilibrium in chemical and physical systems, explaining how equilibrium is reached when the rates of forward and reverse reactions are equal. It also discusses entropy and enthalpy, emphasizing the differences in activation energy for forward and reverse reactions, and provides examples of spontaneous and non-spontaneous reactions such as combustion and photosynthesis. Additionally, it defines key terms related to open and closed systems, dynamic and static equilibrium, and reversible reactions.

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5 views3 pages

Equilibrium in Chemistry Explained

The document covers the concepts of static and dynamic equilibrium in chemical and physical systems, explaining how equilibrium is reached when the rates of forward and reverse reactions are equal. It also discusses entropy and enthalpy, emphasizing the differences in activation energy for forward and reverse reactions, and provides examples of spontaneous and non-spontaneous reactions such as combustion and photosynthesis. Additionally, it defines key terms related to open and closed systems, dynamic and static equilibrium, and reversible reactions.

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Chemistry Module 5 Notes

5.1 – Static and Dynamic Equilibrium


(21.10)
The state of equilibrium is reached in a closed system when the rates of
the forward and reverse reactions are equal.

e.g. H2O (g) ⇌ H2O (l)


This can occur for chemical reactions as well as physical systems,

Dynamic Equilibrium
This is normally how we refer to equilibrium. The forward reaction and the
backward reaction are both occurring and the rate of forward rection =
rate of backward reaction.
e.g. Saturated solutions with crystals (rate of dissolving = rate of
crystalising); water in a waterproof bottle; reaction mixture of gases in an
enclosed container…

Static Equilibrium
This is an unusual type of equilibrium which occurs when the forward and
backward rates are effectively zero.
e.g. Converting graphite to diamond

Non-Equilibrium Systems
Some chemical reactions never reach an equilibrium state such as
combustion reactions or photosynthesis, even in a closed system

Exchanges in Systems:
When in closed systems, energy can only be exchanged with the
surroundings; in open systems, both matter and energy can be changed.

Reaching Equilibrium
As the reaction starts, there are more molecules of reactants than
products, therefore there is more chance of a successful collision of
reactants to produce products
- As the reactant concentration decreases, the rate of the forward reaction
slows
- As the product concentration increases, there are molecules of product
available to collide and reform the reactants, the rate of the reverse
reaction increases
Eventually, the rate of the forward reaction becomes equal to the rate of
the reverse reaction

*Concentrations of reactants and products stay the same throughout the


reaction
*There are no macroscopic changes (pH, colour, pressure, temperature)
*Reactions are ongoing in both direction – the equilibrium is dynamic
(24.10)
Entropy and Enthalpy
Change in enthalpy describes the change in heat energy of a system whereas
change in entropy describes the change in the way the energy is distributed.

Activation energy of equilibrium (forward/reverse) reactions are different but the


ΔH remains the same magnitude, but the sign is reversed for the reverse

E.g. H2 (g) + I2 (g) ⇌ 2HI (g)


reaction.
ΔH= -9.48kJ
Therefore, the reverse reaction would be ΔH=+9.48kJ

ΔG (Gibbs free energy) must be <0 for a reaction to be spontaneous


- The equation ΔG = ΔH – TΔS (T has to be in Kelvin {K})

Combustion Reactions

∴ Combustion reactions are spontaneous with ΔG<0


ΔH < 0, because exothermic

The products of organic combustion, CO 2 and H2O are very stable and do not
recombine to form reactants. These are spontaneous non-equilibrium systems.

Photosynthesis
Contains light-dependent & light-independent stage
-Endothermic (requires light energy to run)
ΔH = +2803kJmol-1
Also, photosynthesis increases order by converting a larger number of liquid and
gas molecules to an aqueous molecule and gas molecules. -> negative ΔS : -
212JK-1mol-1

Substituting into the ΔG= ΔH - T ΔS equation, the following steps need to be


taken:
 ΔS needs to be converted to -0.212 kJK-1mol-1
 T need to be converted to K (assume 25℃ -> 298.15K)
ΔG = 2803 – (298.15 x -0.212) = 2866 kJmol-1, non-spontaneous

{Glossary Page}

Open system A system that can exchange both matter and energy
with its surroundings.
Closed system A system that can exchange energy but not matter
with its surroundings.
Dynamic A state in a reversible reaction where the forward and
Equilibrium reverse reactions occur at the same rate, so the
concentrations of reactants and products remain
constant.
Static A situation where no movement or reaction occurs; all
Equilibrium forces or changes are balanced, and the system is
almost at rest.
Reversible A chemical reaction that can proceed in both the
reaction forward and reverse directions, forming reactants
from products and vice versa. (represent using double
arrow)

Common questions

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Photosynthesis is non-spontaneous as it requires a high positive 9;H of +2803 kJmol-1 due to energy input (light) and shows a negative 9;S, indicating increased order. Calculating 9;G using ambient conditions (9;G = 2866 kJmol-1) confirms it's non-spontaneous. Environmental conditions (sunlight) provide necessary energy, allowing this essential process to occur naturally .

A reaction is spontaneous if the change in Gibbs free energy (9;G) is less than zero. The equation 9;G = 9;H - T9;S combines enthalpy (9;H), temperature (T in Kelvin), and entropy change (9;S). A negative 9;G indicates the total energy available to perform work, implying the reaction can proceed without additional energy input .

In a closed system, equilibrium reactions are influenced mainly by changes in energy (temperature), while matter remains constant. However, in an open system, both matter and energy exchanges with the surroundings alter reaction equilibrium, potentially shifting equilibrium positions or preventing steady-state equilibrium from establishing, due to continuous input or removal of reactants/products .

As the concentration of reactants initially decreases, the forward reaction rate slows due to fewer available molecules for successful collisions. Meanwhile, increasing product concentration elevates the reverse reaction rate. Equilibrium is achieved when both forward and reverse reaction rates become equal, maintaining constant concentrations of reactants and products despite ongoing reactions .

Combustion reactions are highly exothermic, releasing a significant amount of energy, resulting in a negative 9;H. The products CO2 and H2O are thermodynamically stable, making it unlikely for the reverse reaction to occur. Thus, combustion reactions are spontaneous and remain non-equilibrium systems, even when in a closed system .

Temperature affects the T9;S term in the Gibbs free energy equation 9;G = 9;H - T9;S. For photosynthesis, which has a positive 9;H and negative 9;S, an increase in temperature results in T9;S becoming less negative, hence reducing 9;G, making the reaction less non-spontaneous. However, since photosynthesis is inherently non-spontaneous at standard conditions (25B0C, 9;G calculated as 2866 kJmol-1), increasing temperature may not necessarily induce spontaneity at practical temperatures .

Activation energy determines the rate at which reactants form products (forward reaction) and vice versa (reverse reaction) in a dynamic equilibrium. Although the magnitudes of 9;H are the same with opposite signs for forward and reverse reactions, the differing activation energies affect rate kinetics, influencing how quickly equilibrium is reached but not the equilibrium constant itself. Catalysts can lower activation energy, expediting equilibrium attainment .

Enthalpy (9;H) indicates the heat energy change of a system. Exothermic reactions release energy (9;H < 0), often favoring equilibrium formation of products as with combustion. Conversely, endothermic reactions absorb energy (9;H > 0), requiring continuous energy input, such as in photosynthesis. These differences in enthalpy influence whether equilibrium can be easily reached or maintained .

Reaction spontaneity is governed by the interplay between enthalpy (9;H) and entropy (9;S) as summarized by Gibbs free energy (9;G = 9;H - T9;S). A reaction is spontaneous when 9;G < 0, achievable when 9;H is sufficiently negative (exothermic) or when 9;S encourages dispersion of energy (9;S positive or 9;H smaller negative than T9;S). Entropy increment often facilitates endothermic reactions toward spontaneity at high temperatures. Thus, 9;H and 9;S combined provide a comprehensive thermodynamic pathway determining reaction spontaneity .

Dynamic equilibrium occurs when the rates of forward and reverse reactions are equal, and the reactions continue to occur in both directions without macroscopic change, maintaining constant concentrations of reactants and products. In contrast, static equilibrium is when both forward and reverse reaction rates are effectively zero; the system is at rest without changes occurring, such as in the conversion of graphite to diamond .

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