Spontaneous process
Encyclopedia
A spontaneous process is the time-evolution of a system
in which it releases free energy
(usually as heat) and moves to a lower, more thermodynamically stable energy state. The sign convention of changes in free energy follows the general convention for thermodynamic measurements, in which a release of free energy from the system corresponds to a negative change in free energy, but a positive change for the surroundings.
A spontaneous process is capable of proceeding in a given direction, as written or described, without needing to be driven by an outside source of energy. The term is used to refer to macro processes in which entropy
increases; such as a smell diffusing in a room, ice melting in lukewarm water, salt dissolving in water, and iron rusting.
The laws of thermodynamics
govern the direction of a spontaneous process, ensuring that if a sufficiently large number of individual interactions (like atom
s colliding) are involved then the direction will always
be in the direction of increased entropy (since entropy increase is a statistical phenomenon).
is:
The sign of ΔG depends on the signs of the changes in enthalpy
(ΔH) and entropy
(ΔS), as well as on the absolute temperature (T, in kelvin
). ΔG changes from positive to negative (or vice versa) where
T = ΔH/ΔS.
For heterogeneous systems where all of the species of the reaction are in different phases and can be mechanically separated, the following is true.
When ΔG is negative, a process or chemical reaction proceeds spontaneously in the forward direction.
When ΔG is positive, the process proceeds spontaneously in reverse.
When ΔG is zero, the process is already in equilibrium, with no net change taking place over time.
We can further distinguish four cases within the above rule just by examining the signs of the two terms on the right side of the equation.
For Homogeneous systems where all of the species of the reaction are in the same phase, ΔG cannot accurately predict reaction spontaneity.
The second law of thermodynamics
states that for any spontaneous process the overall ΔS must be greater than or equal to zero, yet a spontaneous chemical reaction can result in a negative change in entropy. This does not contradict the second law, however, since such a reaction must have a sufficiently large negative change in enthalpy (heat energy) that the increase in temperature of the reaction surroundings (considered to be part of the system in thermodynamic terms) results in a sufficiently large increase in entropy that overall the change in entropy is positive. That is, the ΔS of the surroundings increases enough because of the exothermicity of the reaction that it overcompensates for the negative ΔS of the system, and since the overall ΔS = ΔSsurroundings + ΔSsystem, the overall change in entropy is still positive.
Another way to view the fact that some spontaneous chemical reactions can lead to products with lower entropy is to realize that the second law states that entropy of an isolated system must increase (or remain constant). Since a negative enthalpy change in a reaction means that energy is being released to the surroundings, then the 'isolated' system includes the chemical reaction plus its surroundings. This means that the heat release of the chemical reaction sufficiently increases the entropy of the surroundings such that the overall entropy of the isolated system increases in accordance with the second law of thermodynamics.
Spontaneity does not imply that the reaction proceeds with great speed. For example, the decay of diamonds into graphite is a spontaneous process occurs very slowly, taking millions of years. The rate of a reaction is independent of its spontaneity, and instead depends on the chemical kinetics
of the reaction. Every reactant in a spontaneous process has a tendency to form the corresponding product. This tendency is related to stability. Stability is gained by a substance if it is in a minimum energy state or is in maximum randomness. Only one of these can be applied at a time. e.g. Water converting to ice is a spontaneous process because ice is more stable since it is of lower energy. However, the formation of water is also a spontaneous process as water is the more random state.
System
System is a set of interacting or interdependent components forming an integrated whole....
in which it releases free energy
Gibbs free energy
In thermodynamics, the Gibbs free energy is a thermodynamic potential that measures the "useful" or process-initiating work obtainable from a thermodynamic system at a constant temperature and pressure...
(usually as heat) and moves to a lower, more thermodynamically stable energy state. The sign convention of changes in free energy follows the general convention for thermodynamic measurements, in which a release of free energy from the system corresponds to a negative change in free energy, but a positive change for the surroundings.
A spontaneous process is capable of proceeding in a given direction, as written or described, without needing to be driven by an outside source of energy. The term is used to refer to macro processes in which entropy
Entropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only be driven by convertible energy, and have a theoretical maximum efficiency when...
increases; such as a smell diffusing in a room, ice melting in lukewarm water, salt dissolving in water, and iron rusting.
The laws of thermodynamics
Laws of thermodynamics
The four laws of thermodynamics summarize its most important facts. They define fundamental physical quantities, such as temperature, energy, and entropy, in order to describe thermodynamic systems. They also describe the transfer of energy as heat and work in thermodynamic processes...
govern the direction of a spontaneous process, ensuring that if a sufficiently large number of individual interactions (like atom
Atom
The atom is a basic unit of matter that consists of a dense central nucleus surrounded by a cloud of negatively charged electrons. The atomic nucleus contains a mix of positively charged protons and electrically neutral neutrons...
s colliding) are involved then the direction will always
Almost surely
In probability theory, one says that an event happens almost surely if it happens with probability one. The concept is analogous to the concept of "almost everywhere" in measure theory...
be in the direction of increased entropy (since entropy increase is a statistical phenomenon).
Overview
For a reaction at constant temperature and pressure, ΔG in the Gibbs free energyGibbs free energy
In thermodynamics, the Gibbs free energy is a thermodynamic potential that measures the "useful" or process-initiating work obtainable from a thermodynamic system at a constant temperature and pressure...
is:
The sign of ΔG depends on the signs of the changes in enthalpy
Enthalpy
Enthalpy is a measure of the total energy of a thermodynamic system. It includes the internal energy, which is the energy required to create a system, and the amount of energy required to make room for it by displacing its environment and establishing its volume and pressure.Enthalpy is a...
(ΔH) and entropy
Entropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only be driven by convertible energy, and have a theoretical maximum efficiency when...
(ΔS), as well as on the absolute temperature (T, in kelvin
Kelvin
The kelvin is a unit of measurement for temperature. It is one of the seven base units in the International System of Units and is assigned the unit symbol K. The Kelvin scale is an absolute, thermodynamic temperature scale using as its null point absolute zero, the temperature at which all...
). ΔG changes from positive to negative (or vice versa) where
T = ΔH/ΔS.
For heterogeneous systems where all of the species of the reaction are in different phases and can be mechanically separated, the following is true.
When ΔG is negative, a process or chemical reaction proceeds spontaneously in the forward direction.
When ΔG is positive, the process proceeds spontaneously in reverse.
When ΔG is zero, the process is already in equilibrium, with no net change taking place over time.
We can further distinguish four cases within the above rule just by examining the signs of the two terms on the right side of the equation.
When ΔS is positive and ΔH is negative, a process is spontaneous
When ΔS is positive and ΔH is positive, a process is spontaneous at high temperatures, where exothermic
ExothermicIn thermodynamics, the term exothermic describes a process or reaction that releases energy from the system, usually in the form of heat, but also in the form of light , electricity , or sound...
ity plays a small role in the balance.
When ΔS is negative and ΔH is negative, a process is spontaneous at low temperatures, where exothermicity is important.
When ΔS is negative and ΔH is positive, a process is not spontaneous at any temperature, but the reverse process is spontaneous.
For Homogeneous systems where all of the species of the reaction are in the same phase, ΔG cannot accurately predict reaction spontaneity.
The second law of thermodynamics
Second law of thermodynamics
The second law of thermodynamics is an expression of the tendency that over time, differences in temperature, pressure, and chemical potential equilibrate in an isolated physical system. From the state of thermodynamic equilibrium, the law deduced the principle of the increase of entropy and...
states that for any spontaneous process the overall ΔS must be greater than or equal to zero, yet a spontaneous chemical reaction can result in a negative change in entropy. This does not contradict the second law, however, since such a reaction must have a sufficiently large negative change in enthalpy (heat energy) that the increase in temperature of the reaction surroundings (considered to be part of the system in thermodynamic terms) results in a sufficiently large increase in entropy that overall the change in entropy is positive. That is, the ΔS of the surroundings increases enough because of the exothermicity of the reaction that it overcompensates for the negative ΔS of the system, and since the overall ΔS = ΔSsurroundings + ΔSsystem, the overall change in entropy is still positive.
Another way to view the fact that some spontaneous chemical reactions can lead to products with lower entropy is to realize that the second law states that entropy of an isolated system must increase (or remain constant). Since a negative enthalpy change in a reaction means that energy is being released to the surroundings, then the 'isolated' system includes the chemical reaction plus its surroundings. This means that the heat release of the chemical reaction sufficiently increases the entropy of the surroundings such that the overall entropy of the isolated system increases in accordance with the second law of thermodynamics.
Spontaneity does not imply that the reaction proceeds with great speed. For example, the decay of diamonds into graphite is a spontaneous process occurs very slowly, taking millions of years. The rate of a reaction is independent of its spontaneity, and instead depends on the chemical kinetics
Chemical kinetics
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition...
of the reaction. Every reactant in a spontaneous process has a tendency to form the corresponding product. This tendency is related to stability. Stability is gained by a substance if it is in a minimum energy state or is in maximum randomness. Only one of these can be applied at a time. e.g. Water converting to ice is a spontaneous process because ice is more stable since it is of lower energy. However, the formation of water is also a spontaneous process as water is the more random state.
See also
- Endergonic reactionEndergonic reactionIn chemical thermodynamics, an endergonic reaction is a chemical reaction in which the standard change in free energy is positive, and energy is absorbed...
reactions which are not spontaneous at standard temperature, pressure, and concentrations. - DiffusionDiffusionMolecular diffusion, often called simply diffusion, is the thermal motion of all particles at temperatures above absolute zero. The rate of this movement is a function of temperature, viscosity of the fluid and the size of the particles...
spontaneous phenomena that minimize Gibbs free energy.