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Gibbs free energy change (G)
]\] thermodynamic property defined in terms of system enthalpy and entropy;
all spontaneous processes involve a decrease in G

microstate
possible configuration or arrangement of matter and energy within a system

nonspontaneous process
process that requires continual input of energy from an external source

reversible process
process that takes place so slowly as to be capable of reversing direction in
response to an infinitesimally small change in conditions; hypothetical
construct that can only be approximated by real processes

second law of thermodynamics

all spontaneous processes involve an increase in the entropy of the universe

spontaneous change
process that takes place without a continuous input of energy from an external
source

standard entropy (S°)

entropy for one mole of a substance at 1 bar pressure; tabulated values are
usually determined at 298.15 K

standard entropy change (ΔS°)

change in entropy for a reaction calculated using the standard entropies

standard free energy change (ΔG°)

change in free energy for a process occurring under standard conditions (1 bar
pressure for gases, 1 M concentration for solutions)

standard free energy of formation (ΔG∘f)(ΔGf°)

change in free energy accompanying the formation of one mole of substance
from its elements in their standard states

third law of thermodynamics

entropy of a perfect crystal at absolute zero (0 K) is zero
 16.1 Spontaneity

Chemical and physical processes have a natural tendency to occur in one direction under certain
conditions. A spontaneous process occurs without the need for a continual input of energy from
some external source, while a nonspontaneous process requires such. Systems undergoing a
spontaneous process may or may not experience a gain or loss of energy, but they will experience a
change in the way matter and/or energy is distributed within the system.
16.2 Entropy
Entropy (S) is a state function that can be related to the number of microstates for a system (the
number of ways the system can be arranged) and to the ratio of reversible heat to kelvin
temperature. It may be interpreted as a measure of the dispersal or distribution of matter and/or
energy in a system, and it is often described as representing the “disorder” of the system.
For a given substance, entropy depends on phase with Ssolid < Sliquid < Sgas. For different substances
in the same physical state at a given temperature, entropy is typically greater for heavier atoms or
more complex molecules. Entropy increases when a system is heated and when solutions form.
Using these guidelines, the sign of entropy changes for some chemical reactions and physical
changes may be reliably predicted.
16.3 The Second and Third Laws of Thermodynamics
The second law of thermodynamics states that a spontaneous process increases the entropy of the
universe, Suniv > 0. If ΔSuniv < 0, the process is nonspontaneous, and if ΔSuniv = 0, the system is at
equilibrium. The third law of thermodynamics establishes the zero for entropy as that of a perfect,
pure crystalline solid at 0 K. With only one possible microstate, the entropy is zero. We may
compute the standard entropy change for a process by using standard entropy values for the
reactants and products involved in the process.
16.4 Free Energy
Gibbs free energy (G) is a state function defined with regard to system quantities only and may be
used to predict the spontaneity of a process. A negative value for ΔG indicates a spontaneous
process; a positive ΔG indicates a nonspontaneous process; and a ΔG of zero indicates that the
system is at equilibrium. A number of approaches to the computation of free energy changes are
possible.
 Gibbs Free Energy Formula: Explained With Derivation and
Solved Examples

When we provide some heat to a system, not all the energy supplied goes to work for expanding the
volume of the system, some quantity of the energy also goes into increasing the internal energy, and
the remaining part is 'non-expansion work'. Let’s understand this through a simple example.
Consider the electrolysis of water to produce hydrogen and oxygen gasses that gradually leads to an
increase in the volume of the system. Basically the amount of 'non-expansion work' is done to cause
the decomposition of water, and the quantity of energy is utilized to do this 'non-expansion work' is
referred to as useful energy or Gibbs free energy. In this Physics article, we are going to discuss
Gibbs Free Energy formula along with some solved numericals.

What is Gibbs Free Energy?

Gibbs Free Energy of a system is defined as the thermodynamics quantity of the system,
the decrease in whose value during a process is equal to useful work done by the system.
The term 'free' in Gibbs Free Energy is called free in the sense that some part or quantity
of energy can be actually used to produce some work, rather than that the system is free
to do some work. Gibbs free energy is a state function, hence, it does depend on the path.
The standard Gibbs free energy is denoted by ΔG°. At equilibrium, Gibbs free energy is
zero.
A simple, yet day-to-day application of Gibbs Free Energy can be found in the working
mechanism of the battery. Batteries basically operate on the simple principle of voltage,
and voltage is nothing but simply a “kind” of Gibbs free energy. Here, you can observe, in
action, that the Gibbs free energy is being harnessed to produce work.

Gibbs Free Energy Formula

Gibbs Free Energy of a system can be mathematically expressed as,
G=H−TSG=H−TS
Here,
H is the enthalpy
S is Entropy
T is absolute Temperature
Derivation of Gibbs Free Energy Formula
Let's work on some other forms of energy.
Clearly, we know that,
Gibbs energy, G=H−TSG=H−TS —(1)
Also, Enthalpy, H=U+PVH=U+PV —(2)
From eqs. (1) and (2), we obtained that,
G=U+PV−TSG=U+PV−TS
Free energy change at constant temperature and pressure can be given as:
ΔG=ΔU+PΔV−TΔS∆G=∆U+P∆V−T∆S
ΔG=ΔH−TΔS∆G=∆H−T∆S (ΔH=ΔU+PΔV∆H=∆U+P∆V)
This is Gibbs Helmholtz equation
Make a note that Gibbs Helmholtz equation is used to discuss the driving force, that is the
overall criterion of spontaneity. Since 'H' and 'S' are extensive properties, hence 'G' will
also be an extensive property.]
 Relation Between Gibbs Free Energy and Equilibrium Constant
The relation between Gibbs free energy (ΔG°) and equilibrium constant (K) is given by the
equation:
ΔG° = -RT ln(K)
where R is the gas constant, T is the temperature in Kelvin, ln is the natural logarithm, K is
the equilibrium constant
This equation shows that the Gibbs free energy of a reaction is directly proportional to the
natural logarithm of the equilibrium constant. If the equilibrium constant is large, then ΔG°
will be negative, indicating that the reaction is spontaneous in the forward direction. On
the other hand, if the equilibrium constant is small, then ΔG° will be positive, indicating
that the reaction is non-spontaneous in the forward direction.

Importance of Gibbs Free Energy

in Thermodynamics
Gibbs free energy helps to predict whether a chemical reaction will occur spontaneously
under specific conditions. It takes into account the enthalpy (heat) and entropy (disorder)
changes of a system, which are critical factors in determining the direction of a chemical
reaction.
Gibbs free energy is also used to calculate the equilibrium constant for a chemical
reaction. The equilibrium constant provides information about the extent to which a
reaction will proceed, and whether the reactants or products are more stable under certain
conditions. This information is important for understanding the behavior of chemical
systems in a wide range of fields, including chemistry, biology, and engineering.
Furthermore, Gibbs free energy is used to determine the maximum work that can be
obtained from a system under specific conditions. This information is important for
designing efficient energy conversion processes, such as fuel cells and batteries, and for
optimising industrial processes.

Difference Between Gibbs Free Energy and Helmholtz Free Energy

Some important differences between Gibbs free energy and Helmholtz free energy are as
follows.
Property Gibbs Free Energy Helmholtz Free Energy
Energy available to do work at Energy available to do work at constant
Definition
constant temperature and pressure volume and temperature
Formula ΔG = ΔH - TΔS ΔA = ΔU - TΔS
Joules (J) or kilojoules per mole
Units Joules (J) or kilojoules per mole (kJ/mol)
(kJ/mol)
Predicts if a reaction is spontaneous Determines the maximum work that can be
Significance or not at constant temperature and obtained from a system at constant
pressure temperature and volume
 Applications of Gibbs Free Energy Formula
Some of the important applications of the Gibbs free energy formula are:
 Predicting the spontaneity of chemical reactions: The Gibbs free energy formula is
used to predict whether a chemical reaction will occur spontaneously or not. If the
Gibbs free energy change of a reaction is negative, the reaction will occur
spontaneously, and if it is positive, the reaction will not occur spontaneously.
 Determining the equilibrium constant: The Gibbs free energy formula can be used
to calculate the equilibrium constant of a chemical reaction. The equilibrium
constant gives information about the relative amounts of reactants and products at
equilibrium, and this information is useful in designing chemical processes.
 Designing and optimising chemical processes: The Gibbs free energy formula is
used in the design and optimisation of chemical processes. By knowing the Gibbs
free energy change of a reaction, the maximum amount of work that can be
obtained from the reaction can be calculated, and this information is used to design
more efficient chemical processes.
 Predicting phase changes: The Gibbs free energy formula is used to predict phase
changes in materials. By calculating the Gibbs free energy change of a material, it
can be determined whether the material will exist in a solid, liquid or gaseous state
under specific conditions.
 Predicting and optimising energy storage systems: The Gibbs free energy formula is
used to design and optimize energy storage systems such as batteries, fuel cells,
and thermal storage systems. By knowing the Gibbs free energy change of a
reaction, the maximum amount of energy that can be obtained from the system can
be calculated, and this information is used to design more efficient energy storage
systems.

Limitations of Gibbs Free Energy Formula

The Gibbs free energy formula has some limitations, which include:
 The formula assumes that the reaction is at constant temperature and pressure,
which may not be the case in real-world situations.
 The formula does not take into account the kinetics of the reaction, which is the
rate at which the reaction occurs.
 The formula assumes that the system is in a state of equilibrium, which may not be
true in some cases.
 The formula does not consider the effects of external factors such as catalysts,
which can influence the Gibbs free energy change of a reaction.
 The formula assumes that the system is homogeneous, which may not be true in
some cases where the system is heterogeneous.

Gibbs Free Energy Formula Solved Examples

Example 1. Calculate the ∆G for the reaction if the enthalpy change is 22kJ/mol^{-1}.
Given that there is no entropy change during the reaction.
Solution 1: Given data
∆H = 22kJ/mol
∆S = 0
and, ∆G = ?
Clearly, we know that
∆G = ∆H - T∆S
On substituting the values in the above equation, we obtained,
∆G = 22kJ/mol - T × 0
∆G = 22kJ/mol
Hence, the Gibbs free energy comes out to be 22kJ/mol.
Example 2. Calculate ∆G at 700 K when enthalpy and entropy changes are -130.0kJ/mol
and -145 kJ/mol K\) respectively.
Solution 2: Given data
∆H = -130.0 kJ/mol = -113000 J/mol
∆S = -145 J/mol K
T = 700K
and, ∆G = ?\)
Clearly, we know that
∆G = ∆H - T∆S
On substituting the values in the above equation, we obtained,
∆G = -113000 - 700 × (-145)
∆G = -11500 J/mol
∆G = -11.5 k J/mol
Hence, the change in Gibbs free energy comes out to be -11.5 k J/mol.
Example 3. The enthalpy of the reaction is -12.55 kJ/mol and entropy change equals 5.0
J/K mol for the reaction at temperature 17°C. Calculate the free energy change and predict
whether the reaction is spontaneous or not.
Solution 3:Given data
∆H = -12.55 kJ/mol
∆S = 5.0 J/molK
T = 17°C = 17 + 273 K = 290K
and, ∆G = ?
Clearly, we know that
∆G = ∆H - T∆S
On substituting the values in the above equation, we obtained,
∆G = -12.55 - 0.005 × (-290)
∆G = -14.00k J/mol
Hence, the change in Gibbs free energy comes out to be -11.5 k J/mol.
Example 4. Calculate the temperature at which liquid water is in equilibrium with water
vapor. Given the \)∆H_{vap} = 40.73 kJ/mol and ∆S_{vap} = 0.109 kJ/mol K\)
Solution 4: Given data
∆H = 40.73 kJ/ mol
∆S = 0.109 kJ/ molK
and, ∆G = 0\)
Clearly, we know that
∆G = ∆H - T∆S
On substituting the values in the above equation, we obtained,
0 = 40.73 - T × 0.109
T × 0.109 = 40.73
T=40.730.109T=40.730.109
T = 373.6 K
Hence, the temperature comes out to be 373.6 K.
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Enthalpy vs. Entropy
 Free energy

Google Classroom
Microsoft Teams

The Gibbs free energy change (ΔG) and how it's related to reaction spontaneity
and equilibrium.

Introduction
When you hear the term “free energy,” what do you think of?
Well, if you’re goofy like me, maybe a gas station giving away
gas. Or, better yet, solar panels being used to power a
household for free. There’s even a rock band from Philadelphia
called Free Energy (confirming my longtime suspicion that
many biology terms would make excellent names for rock
bands).

These are not, however, the meanings of “free energy” that

we’ll be discussing in this article. Instead, we’re going to look
at the type of free energy that is associated with a particular
chemical reaction, and which can provide a measure of how
much usable energy is released (or consumed) when that
reaction takes place.

Free energy
A process will only happen spontaneously, without added
energy, if it increases the entropy of the universe as a whole
(or, in the limit of a reversible process, leaves it unchanged) –
this is the Second Law of Thermodynamics. But to me at least,
that's kind of an abstract idea. How can we make this idea
more concrete and use it to figure out if a chemical reaction
will take place?
Basically, we need some kind of metric that captures the effect
of a reaction on the entropy of the universe, including both the
reaction system and its surroundings. Conveniently, both of
these factors are rolled into one convenient value called the
Gibbs free energy.

The Gibbs free energy (G) of a system is a measure of the

amount of usable energy (energy that can do work) in that
system. The change in Gibbs free energy during a reaction
provides useful information about the reaction's energetics and
spontaneity (whether it can happen without added energy). We
can write out a simple definition of the change in Gibbs free
energy as:
In other words, ΔG is the change in free energy of a system as
it goes from some initial state, such as all reactants, to some
other, final state, such as all products. This value tells us the
maximum usable energy released (or absorbed) in going from
the initial to the final state. In addition, its sign (positive or
negative) tells us whether a reaction will occur spontaneously,
that is, without added energy.
When we work with Gibbs free energy, we have to make some
assumptions, such as constant temperature and pressure;
however, these conditions hold roughly true for cells and other
living systems.
 Gibbs free energy, enthalpy, and
entropy
In a practical and frequently used form of Gibbs free energy
change equation, ΔG is calculated from a set values that can
be measured by scientists: the enthalpy and entropy changes
of a reaction, together with the temperature at which the
reaction takes place.
Let’s take a step back and look at each component of this
equation.

 ∆H is the enthalpy change. Enthalpy in biology refers to

energy stored in bonds, and the change in enthalpy is the
difference in bond energies between the products and the
reactants. A negative ∆H means heat is released in going from
reactants to products, while a positive ∆H means heat is
absorbed. (This interpretation of ∆H assumes constant
pressure, which is a reasonable assumption inside a living cell).
 ∆S is the entropy change of the system during the reaction. If
∆S is positive, the system becomes more disordered during the
reaction (for instance, when one large molecule splits into
several smaller ones). If ∆S is negative, it means the system
becomes more ordered.
 Temperature (T) determines the relative impacts of the ∆S and
∆H terms on the overall free energy change of the reaction.
(The higher the temperature, the greater the impact of the
∆S term relative to the ∆H term.) Note that temperature needs
to be in Kelvin (K) here for the equation to work properly.
Reactions with a negative ∆G release energy, which means that
they can proceed without an energy input (are spontaneous).
In contrast, reactions with a positive ∆G need an input of
energy in order to take place (are non-spontaneous). As you
can see from the equation above, both the enthalpy change
and the entropy change contribute to the overall sign and
value of ∆G. When a reaction releases heat (negative ∆H) or
increases the entropy of the system, these factors make
∆G more negative. On the other hand, when a reaction absorbs
heat or decreases the entropy of the system, these factors
make ∆G more positive.
By looking at ∆H and ∆S, we can tell whether a reaction will be
spontaneous, non-spontaneous, or spontaneous only at certain
temperatures. If a reaction both releases heat and increases
entropy, it will always be spontaneous (have a negative ∆G),
regardless of temperature. Similarly, a reaction that both
absorbs heat and decreases entropy will be non-spontaneous
(positive ∆G) at all temperatures. Some reactions, however,
have a mix of favorable and unfavorable properties (releasing
heat but decreasing entropy, or absorbing heat but increasing
entropy). The ∆G and spontaneity of these reactions will
depend on temperature, as summarized in the table at right.
Why can these terms predict spontaneity?

Endergonic and exergonic

reactions
Reactions that have a negative ∆G release free energy and are
called exergonic reactions. (Handy mnemonic: EXergonic
means energy is EXiting the system.) A negative ∆G means
that the reactants, or initial state, have more free energy than
the products, or final state. Exergonic reactions are also
called spontaneous reactions, because they can occur
without the addition of energy.
Reactions with a positive ∆G (∆G > 0), on the other hand,
require an input of energy and are called endergonic
reactions. In this case, the products, or final state, have more
free energy than the reactants, or initial state. Endergonic
reactions are non-spontaneous, meaning that energy must be
added before they can proceed. You can think of endergonic
reactions as storing some of the added energy in the higher-
energy products they form.
It’s important to realize that the word spontaneous has a very
specific meaning here: it means a reaction will take place
without added energy, but it doesn't say anything about how
quickly the reaction will happen. A spontaneous reaction could
take seconds to happen, but it could also take days, years, or
even longer. The rate of a reaction depends on the path it
takes between starting and final states (the purple lines on the
diagrams below), while spontaneity is only dependent on the
starting and final states themselves. We'll explore reaction
rates further when we look at activation energy.
Image credit: OpenStax Biology.

Spontaneity of forward and

reverse reactions
If a reaction is endergonic in one direction (e.g., converting
products to reactants), then it must be exergonic in the other,
and vice versa. As an example, let’s consider the synthesis and
breakdown of the small molecule adenosine triphosphate (),
which is the "energy currency" of the cell.

is made from adenosine diphosphate () and phosphate ()

according to the following equation:
+ +

This is an endergonic reaction, with ∆G = under standard

conditions (meaning concentrations of all reactants and
products, pressure, degrees , and of ). In the cells of your
body, the energy needed to make is provided by the
breakdown of fuel molecules, such as glucose, or by other
reactions that are energy-releasing (exergonic).
The reverse process, the hydrolysis (water-mediated
breakdown) of , is identical but with the reaction flipped
backwards:

+ +

This is an exergonic reaction, and its ∆G is identical in

magnitude and opposite in sign to that of the ATP synthesis
reaction (∆G = under standard conditions). This relationship of
same magnitude and opposite signs will always apply to the
forward and backward reactions of a reversible process.

Non-standard conditions and

chemical equilibrium
You may have noticed that in the above section, I was careful
to mention that the ∆G values were calculated for a particular
set of conditions known as standard conditions. The standard
free energy change (∆Gº’) of a chemical reaction is the
amount of energy released in the conversion of reactants to
products under standard conditions. For biochemical reactions,
standard conditions are generally defined
as ( ), concentrations of all reactants and
products, pressure, and of (the prime mark in ∆Gº’ indicates
that is included in the definition).
The conditions inside a cell or organism can be very different
from these standard conditions, so ∆G values for biological
reactions in vivo may vary widely from their standard free
energy change (∆Gº’) values. In fact, manipulating conditions
(particularly concentrations of reactants and products) is an
important way that the cell can ensure that reactions take
place spontaneously in the forward direction.

Chemical equilibrium
To understand why this is the case, it’s useful to bring up the
concept of chemical equilibrium. As a refresher on chemical
equilibrium, let’s imagine that we start a reversible reaction
with pure reactants (no product present at all). At first, the
forward reaction will proceed rapidly, as there are lots of
reactants that can be converted into products. The reverse
reaction, in contrast, will not take place at all, as there are no
products to turn back into reactants. As product accumulates,
however, the reverse reaction will begin to happen more and
more often.

This process will continue until the reaction system reaches a

balance point, called chemical equilibrium, at which the
forward and reverse reactions take place at the same rate. At
this point, both reactions continue to occur, but the overall
concentrations of products and reactants no longer change.
Each reaction has its own unique, characteristic ratio of
products to reactants at equilibrium.
When a reaction system is at equilibrium, it is in its lowest-
energy state possible (has the least possible free energy). If a
 reaction is not at equilibrium, it will move spontaneously
towards equilibrium, because this allows it to reach a lower-
energy, more stable state. This may mean a net movement in
the forward direction, converting reactants to products, or in
the reverse direction, turning products back into reactants.

As the reaction moves towards equilibrium (as the

concentrations of products and reactants get closer to the
equilibrium ratio), the free energy of the system gets lower and
lower. A reaction that is at equilibrium can no longer do any
work, because the free energy of the system is as low as
possible. Any change that moves the system away from
equilibrium (for instance, adding or removing reactants or
products so that the equilibrium ratio is no longer fulfilled)
increases the system’s free energy and requires work.

How cells stay out of equilibrium

If a cell were an isolated system, its chemical reactions would
reach equilibrium, which would not be a good thing. If a cell's
reaction reached equilibrium, the cell would die because there
would be no free energy left to perform the work needed to
keep it alive.

Cells stay out of equilibrium by manipulating concentrations of

reactants and products to keep their metabolic reactions
running in the right direction. For instance:

 They may use energy to import reactant molecules

(keeping them at a high concentration).
 They may use energy to export product molecules
(keeping them at a low concentration).

 They may organize chemical reactions into metabolic

pathways, in which one reaction "feeds" the next.

Providing a high concentration of a reactant can "push" a

chemical reaction in the direction of products (that is, make it
run in the forward direction to reach equilibrium). The same is
true of rapidly removing a product, but with the low product
concentration "pulling" the reaction forward. In a metabolic
pathway, reactions can "push" and "pull" each other because
they are linked by shared intermediates: the product of one
step is the reactant for the next.
 Gibb's Free Energy
Free energy is a concept that we have invented to incorporate the entropy change for the
surroundings into a change in a state function of the system. Free energy is a way for us to
think about the 2nd Law of thermodynamics only from the perspective of the system.
The second law states that for a process to be spontaneous it must increase the entropy of
the universe.
ΔSuniv=ΔSsys+ΔSsurr>0
If we invoke certain conditions, we can rewrite this equation. First we will look at constant
pressure, which is a natural condition for chemistry. At constant pressure the heat is
simply the change in entropy of the system. Since the change in the entropy of the
surrounding is related to the heat, we can now write this in terms of the enthalpy change
of the system. We can also look at conditions of constant temperature so the entropy
change of the surroundings can simply be related to the enthalpy change of the system.
ΔSsurr=−qT=−ΔHsysT
We can now rewrite our 2nd Law equation
ΔStotal=ΔSsys+ΔSsurr=ΔSsys−ΔHsysT>0
Now everything is in terms of the system (so we can drop the system subscript). This is, in
a way, a small victory. We could be finished here, but our 2nd Law equation is still in
entropy terms. We don't like to think in terms of entropy we would rather think in terms of
energy. We can get to energy units if we simply multiply through by T.
TΔS−ΔH>0
We could again be done here. However, we now have an energy that increases for
spontaneous processes. That seems counter intuitive. So we multiply the whole equation
by a minus. This yields
ΔH−TΔS<0
Introducing a new State Function (variable) - Gibb's Free Energy We now have an
energy term for the system which will decrease for a spontaneous process (at constant
temperature and pressure). We can define this new state variable to reflect this energy.
The new variable is the Gibb's Free Energy, G:
G=H−TS
This is the definition of the Gibb's Free Energy which will allow us to predict the
spontaneity of a reaction using all system-based variables. This allows us to rewrite the
second law based on only a system state function, ΔG. For a spontaneous process for an
isolated system (at constant temperature and pressure) the change in free energy must be
negative.
forspontaneouschange:ΔG<0

We can use these ideas for find the standard Gibb's Energy change for a chemical change.
Free energy is a state function and therefore can be calculated via the free energies of
formation of the reactants and products just like the enthalpy of reaction was:
ΔGrxn∘=∑nΔGf∘(products)−∑nΔGf∘(reactants)
Most thermodynamic tables include ΔHf∘, ΔGf∘, and ΔS∘, but sometimes you might NOT
have ΔGf∘ (like on an exam) and you should know how to
calculate ΔG from ΔH and ΔS using the familiar equation:
ΔG=ΔH−TΔS
The standard version looks like this:
ΔG∘=ΔH∘−TΔS∘

Spontaneity
If something (reaction or process) lowers the free energy, we say such a process is
"spontaneous." That simply means it will tend to happen - much like a ball tends to roll
downhill. The reverse of this situation is also evident - if a process is "not spontaneous,"
then it will tend to not happen. This isn't to say that non-spontaneous
processes/reactions never happen, it is just that if they are to happen, some external
amount of work must be applied to make the process happen - much like physically taking
the ball up the hill to a higher position (the ball will never do this without the aid of applied
work).

So when we say "it will never happen" for a non-spontaneous process. What we mean is it
will "never happen in isolation." If you can combine this process with another one that is
spontaneous, then you can make the total or net process spontaneous.
In chemistry, we are often looking at reactions. For these, we compare the pure products
and the pure reactants (in their standard state). This comparison gives us the standard
change in free energy for a reaction. If this standard free energy change is negative at a
given temperature then we would call it "spontaneous." If it is positive, then it is not
spontaneous (the reverse reaction is spontaneous). The standard change tells us about the
spontaneity of going from all reactants to all products. However, in the real world reactions
"end" somewhere in between these two extremes. This is an important concept called
chemical equilibrium. Therefore, we say for reactions that are spontaneous (−ΔG) "favor
the products" side of the equation; those that are not spontaneous (+ΔG) "favor the
reactants."

Equilibrium
First, a kinetic view of Equilibrium
Chemical equilibrium is an example of a dynamic equilibrium and not static equilibrium.
Know the difference in the two. Static equilibrium is fixed and non-changing – like
balancing weights on a balance beam. Dynamic equilibrium has no NET overall change but
does have some given processes still proceeding. The process itself proceeds both
forwards and backwards at exactly the same rate. Anything that you are constantly
depleting via one process is simultaneously being replenished by another process. Stated
chemically, equilibrium is achieved when the forward rate of reaction equals the reverse
rate of reaction. That is a purely kinetic argument for equilibrium and we will study
reaction kinetics (rates) in the second half of general chemistry (CH302). A complete
understanding of equilibrium requires knowledge of both arguments (definitions) for the
equilibrium state. This unit is about thermodynamics, which has our other definition of
equilibrium. It is based purely on thermodynamic state functions. Lets get the
thermodynamic argument for equilibrium established next.
Thermodynamic Equilibrium
The bottom line for the thermodynamic argument lies in the spontaneity of a reaction. The
Second Law of Thermodynamics dictates what direction of change is the spontaneous
direction. We know that indicator to be universal entropy (ΔSuniv), although in the
previous section we showed how the free energy change (ΔG) is an even better indicator
for us because it is a purely system based state function. Once again, lets look at the
definition of G.
G=H−TS
You'll notice that G is made up from 3 other state functions. Also pay close attention to
how G will change with T. LOOK at the equation, as T increases, G must decrease. If we
hold temperature (T) and pressure (P) constant, we get the following for the change in free
energy:
ΔG=ΔH−TΔS
This powerful formula allows us to track spontaneity with a purely system state
function, ΔG. It tracks via sign the opposite of the way that ΔSuniv does
because ΔG=−TΔSuniv. Now consider the 3 possible mathematical outcomes for ΔG:
ΔG<0
⊖ negative
spontaneous
ΔG=0
zero
equilibrium
ΔG>0
⊕ positive
non-spontaneous
We now have a new standard to judge spontaneity and equilibrium. ALL equilibrium
processes must have a free energy change equal to zero. This is the same as saying that
all the free energies (that’s plain ol’ G here) of all the reactants must equal the free
energies of all the products – our “stalemate” condition for equilibrium.

Notice How the Signs of ΔH and ΔS Affect ΔG

Notice how ΔG’s sign is controlled by the signs on ΔH and ΔS. There are four distinct cases
here. The following plot shows each of these cases:
Note there are only 2 of those cases where equilibrium is even possible; those are the
cases where the 2 plots cross the zero-point for ΔG. This is only when ΔH and ΔS have
matching signs. Remember that we typically control the temperature of the reactions that
we are running. Note how by controlling temperature, we, in effect, control the spontaneity
as well.

More on Phase Transitions

Phase transitions occurring at their standard temperature (ice melting at 0 °C are
reversible equilibrium processes. If you have an equilibrium process occurring,
then ΔG=0 and therefore at these temperatures
ΔH=TΔS ΔS=ΔHT T=ΔHΔS
For example, for water ΔSfusion=(ΔHfusion/273.15K) since the temperature for the phase
transition is 0 °C (273.15 K). You can also use this idea to find the phase transition
temperature if you know the enthalpy and the entropy changes.
Introduction to Gibbs Free EnergyThe Gibbs free energy, also
commonly known as the Gibbs function, Gibbs energy, or free
enthalpy, is a thermodynamic potential that is used to measure the
maximum amount of work done in any given thermodynamic system
when the temperature and pressure of the system are kept constant.
Gibbs free energy is denoted by the letter G. Its value is usually
expressed in either Joules or Kilojoules as it is also a form of energy.
Gibbs free energy is defined as the maximum amount of work done
that can be extracted from a closed thermodynamic system.Gibbs
energy is a thermodynamic property and it was determined by
American scientist Josiah Willard Gibbs in the year 1876 when he was
conducting experiments to predict the behaviour of systems when
combined together or whether a process could take place
simultaneously and spontaneously at a given temperature. Gibbs free
energy was also known as available energy. Gibbs free energy can be
visualized as the total amount of useful energy present in a
thermodynamic system that can be utilized to perform some
work.ImagewillbeuploadedsoonImagewillbeuploadedsoonImage will be
uploaded soonGibbs EnergyGibbs energy is also known as Gibbs free
energy, it is one of the four thermodynamic potentials. Gibbs free
energy is equal to the difference in enthalpy of the system with the
product of the temperature and entropy. The equation is given as:G =
H - TSWhere,G = Gibbs free energyH = enthalpyT = temperatureS =
entropyGibbs free energy is a state function thus it doesn’t depend on
the path (i.e., its path independent entity). Thus, the change in Gibbs
free energy will be equal to the difference in the change in enthalpy
with the product of temperature and entropy change of the system.ΔG
= ΔH - Δ(TS)If the reaction is carried out under constant temperature
i.e., assuming that the reaction is isothermal in nature,ΔT=0 then:ΔG
= ΔH - TΔSThis equation is called the Gibbs Helmholtz equation.Now,
depending on the value of the change in Gibbs free energy, we can
define many new reactions:Suppose the change in Gibbs free energy
is greater than zero (ΔG > 0), then the reaction is nonspontaneous
and endergonic.Suppose the change in Gibbs free energy is less than
zero (ΔG < 0), then the reaction is spontaneous and
exergonic.Suppose the change in Gibbs free energy is equal to zero
(ΔG = 0), then the reaction is at equilibrium condition.There are some
important key points to be remembered regarding Gibbs free energy
such as:According to the second law of thermodynamics, the entropy
of the universe always increases for a spontaneous process and it can
never be equal to zero.The change in Gibbs free energy (ΔG)
determines the direction and extent of chemical change.The change in
Gibbs free energy (ΔG) is useful only for reactions in which the
temperature and pressure remain constant (i.e., it is in good
agreement with the isothermal and isobaric process). The system is
usually open to the atmosphere (constant pressure) and we initiate
and terminate the process at room temperature (after any heat we
have supplied or which is released by the reaction has
dissipated).Standard Gibbs free energy is often used as the single
master variable that determines whether a given chemical change is
thermodynamically possible. Thus, if the change in free energy of the
reactants is more than that of the products, the entropy of the world
will increase when the reaction takes place as written, and so the
reaction will tend to take place spontaneously. ΔSuniverse =
ΔSsystem + ΔSsurroundingsIf the change in Gibbs free energy is
negative, the process will occur spontaneously and is referred to as
exergonic.Therefore spontaneity of the reaction is dependent on the
temperature of the system (Gibbs free energy spontaneous).Even
though the change in Gibbs free energy is temperature-dependent, we
assume the change in enthalpy ∆H and the change in entropy ∆S
independent of temperature when there is no phase change in the
reaction. So if we know the change in enthalpy ∆H and the change in
entropy ∆S, we can calculate the change in Gibbs free energy ∆G at
any temperature.Relationship Between Free Energy and Equilibrium
ConstantThe change in Gibbs free energy of the thermodynamic
reaction in any state, ΔG (at equilibrium) is related to the standard
free energy change of the reaction, ΔG° (that is equal to the difference
in the free energies of creation of the products and reactants both in
their standard states) According to the equation:ΔG = ΔG° + RT In
QWhere,Q- The reaction quotient.∆G = 0 and Q become adequate to
the constant. Hence the equation becomes,G0 = -RT ln KeqG0 = -
2.303 RT log KeqWhere,R = gas constant = 8.31 J mol-1 K-1 or
0.008314 kJ mol-1 K-1 T is the temperature on the Kelvin scaleIn any
reversible reaction, the free energy of the reaction mixture is less than
the free energy of reactants also as products. Hence, Gibbs free
energy decreases whether we start from reactants or products i.e, ∆G
is -ve in both backward and the forward reactions.Relationship
Between Gibbs Free Energy and EMF of a CellIn the case of galvanic
cells, Gibbs energy change ΔG is said to be the trade done by the
cell.ΔG = -nFEcellWhere,n = no. of moles of electrons involvedF = the
Faraday constantE = emf of the cellWe know that 1 Faraday = 96500
coulombs.Did You Know?We know that both the enthalpy of the
system and the Gibbs free energy are the thermodynamic potentials,
and one of the unique facts is that even the unit of ∆G is the same as
that of ∆H.The tesla free energy is modern free energy, though it is
named free energy it is not free, it requires components. Usually found
in a free electricity generator or free energy motor.A free energy
generator magnet follows a mechanism that generates electrical
energy using the neodymium magnet theory. There are various sizes
of generators, and one kind of generator that produces electrical
energy is the free energy
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system (Gibbs free energy spontaneous)."}}]}Is this page helpful?

Gibbs Free Energy

What is Gibbs Energy?
Generally, the total entropy change is the fundamental parameter that defines the
spontaneity of any process.
Since most of the chemical reactions fall under the category of a closed system and open system;
we can say there is a change in enthalpy too along with the change in entropy.

Gibbs energy is a state function and an extensive property. Since, change in enthalpy too increases
or decreases the randomness by affecting the molecular motions, entropy change alone cannot
account for the spontaneity of such process. Therefore, we use the Gibbs energy change for
explaining the spontaneity of a process.

Knowledge of the Gibbs energy under one condition compared with another
allows us to predict the direction of spontaneous change or movement: A
spontaneous change in a system at constant temperature and pressure
proceeds in the direction of decreasing free energy.

Expression for Gibbs Energy Change

General expression for Gibbs energy change at constant temperature is
expressed as:
Above equation is popularly known as Gibbs equation. Gibbs’ equation relates
enthalpy and entropy of the system. We know that for a spontaneous process,
the total entropy change, ΔS is greater than zero.

In case of thermal equilibrium between system and surrounding, temperature

change between system and surrounding, ΔT = 0. Hence, we can say that
enthalpy lost by the system is gained by the surrounding. Hence, the entropy
change of the surrounding is given as,

As discussed earlier, for the spontaneity of a process, ΔStotal > 0. Above

equation becomes,
Above equation can be related to Gibbs equation as,
△Gsys<0
On the basis of above equation we can infer:

The Spontaneity of A Process

Gibbs equation helps us to predict the spontaneity of reaction on the basis of
enthalpy and entropy values directly. When the reaction is exothermic,
enthalpy of the system is negative making Gibbs free energy negative. Hence,
we can say that all exothermic reactions are spontaneous.

In the case of endothermic reactions, when enthalpy of the system is positive,

the process is spontaneous under two conditions:
 Temperature is very high to make the Gibbs energy value negative
Entropy change is very high to make the Gibbs free energy negative.

Spontaneity can only indicate if a reaction can occur not necessarily if a

reaction will occur. For example, the conversion of diamond to graphite is a
spontaneous process at Standard Temperature and Pressure (STP) but it is a
slow process. It will take years for the transformation to occur.

Gibbs Energy in Chemistry

The energetics of processes for systems at constant temperature and pressure,
the appropriate quantity is known as the Gibbs free energy. The Gibbs free
energy has a very useful property; it decreases for a spontaneous process at
constant temperature and pressure. Under such conditions the decrease in
Gibbs free energy equals the maximum amount of energy available for work,
whereas if it increases for some transition, the change in Gibbs free energy
represents the minimum amount of work required.

The transformation of a system from one state to another, at constant

temperature and pressure, is spontaneous if the Gibbs free energy decreases.
If the Gibbs free energy is unchanged by the transformation the two states are
in equilibrium. In other words the criterion for the thermodynamic equilibrium
of a system at constant temperature and pressure is that the Gibbs free energy
of the system be at the minimum value. The Gibbs free energy is sometimes
called the thermodynamic potential at constant pressure in order to indicate its
analogy with the potential energy of a mechanical system, which also has a
minimum value under equilibrium conditions.

Frequently Asked Questions – FAQs

Q1

Why is Gibbs free energy called free energy?

The reason Gibbs Energy is referred to as free energy is that for some system
the increase in Gibbs Energy is the maximum possible work that the process
can generate due to constant pressure and temperature in the atmosphere.
Q2
 Why is Gibbs free energy important?
It is important to be able to measure the free energy of Gibbs because you can
use it to determine the likelihood of a reaction. Negative enthalpy and positive
entropy support a potential reaction
Q3

How does Gibbs’s free energy predict spontaneity?

Spontaneity informs us of the path of the reaction, but not how rapidly it is
going. Gibbs free energy is a simple formula that incorporates enthalpy,
entropy, and temperature. G = H — TS. And finally, for a spontaneous reaction,
the delta G sign is ALWAYS negative.
Q4

What is the concept of entropy?

Entropy, the calculation of the thermal energy of a device per unit temperature
inaccessible for useful work. The sum of entropy is also a measure of a
system’s molecular disorder, or randomness since research is derived from
ordered molecular motion.
Q5

What happens when G is equal to zero?

If delta-G zero is zero, let’s write it down here, so if your standard free energy
change, delta-G zero, is zero, K is zero. And that means your products and
reactants are equally favoured in equilibrium.
Q6

When Gibbs free energy is negative?

The ΔG sign will be changed from positive to negative (or vice versa) where T =
ΔH / ΔS is changed. In cases where the subject is: negative, the process is
spontaneous and can proceed as written in the forward direction. Positive, the
process is non-spontaneous as written, but may proceed in the opposite
direction spontaneously.
Q7
 What does a decrease in free energy mean?
If free energy is diminishing, the reaction can continue. If the free energy
grows, the reaction can not proceed. A reaction is favored when the system’s
free energy diminishes. A reaction is not preferred if the system’s free energy
rises.
Q8

How does Gibbs free energy relate to work?

Gibbs free energy measures useful work at a constant temperature and
pressure obtainable from a thermodynamic system. The Gibbs free energy (G)
is equal to the work exchanged by the system with its surroundings when a
system changes from an initial state to a final state, minus the work of the
pressure force.

Standard Gibbs Free Energy Change

The standard Gibbs free energy change is the change of Gibbs free energy that accompanies the
formation of one mole of that substance from its component elements, at their standard states.

Introduction
To explain the changes in both entropy and enthalpy, J. Willard Gibbs has defined a new function
called Gibbs energy change or Gibbs potential G. This function is independent of variation in
pressure and temperature. The change in Gibbs energy depends only on the state of the system, not
on how that state was achieved.
The change in Gibbs energy associated with the formation of a compound from its component
elements under standard conditions is known as the standard Gibbs free energy of formation. The
concepts of free energy of a process like a rate or an equilibrium and the free energy of a standard
process often equilibrium, which may be the process under investigation or other standard reaction.
Standard Gibbs free energy
The maximum work (or reversible) work that can be done by a thermodynamic system at constant
pressure and temperature is known as the Gibbs energy. Reversible work in thermodynamics means
a method where work is performed in such a way that the system is in perfect equilibrium with its
environment. In relation to chemical reactions, the word reversible means that the reaction can be
carried out in both directions simultaneously and a dynamic equilibrium is always maintained. This
further means that reactions should proceed in both directions with a decrease in free energy, which
seems to be impossible. This is only possible if, in equilibrium, the system’s Gibbs energy reaches
its minimum value. Otherwise, the system will spontaneously switches to the configuration of
lower free energy.
 The equation/formula of Gibbs free energy
We can say a thermodynamics system is in equilibrium when it’s intensive properties such as
temperature and pressure and extensive properties (U,G,A) are constant. By seeing the equation
given below we can say that if the reaction is reversible and the Gibbs free energy is zero , then the
system will be in equilibrium.

For endothermic reaction

For a reaction to be endothermic ,the value of change in enthalpy of a reaction (∆rH) is large and
positive , in this the process is spontaneous under two conditions:-
 Temperature should be very high to make the Gibbs free energy value negative.
 Change in entropy should be very high to make the Gibbs free energy negative.
For exothermic reaction
For the reaction to be exothermic , the enthalpy of the system (∆rH) should always be negative
which makes the Gibbs free energy (∆rG) negative.
The unit of Gibbs free energy is KiloJoule . It is usually represented by kJ/mol.
Spontaneity of the reaction
The reaction is favourable which means spontaneous – the value of ΔG is negative.
The reaction is not favourable which means non-spontaneous – the value of ΔG is positive.
The reaction is said to be in equilibrium if the value of gibbs free energy (ΔrG) is zero.
Standard free energy change in biochemical reactions
In biochemical reactions, the standard free energy change is usually expressed as G, which is the
free energy change of a reaction in aqueous solution at pH = 7, which roughly corresponds to the
conditions inside a cell. Most of the biological reactions (such as the synthesis of macromolecules)
are thermodynamically unfavorable (G > 0) under cellular conditions. In order for such reactions to
take place, an additional source of energy is required. For example, consider the reaction :
A⇌B ∆G= -10kJ/mol
The conversion from A to B is energetically unfavorable, so the reaction proceeds in the reverse
direction rather than the forward direction. However, the reaction could be driven in the forward
direction by coupling the A to B conversion with an energetically favorable reaction such as
C ⇌ D , ∆G= +20kJ/mol
When these two reactions are mixed, the coupled reaction can be written as follows:-
A+C ⇌ B+D , ∆G= -10kJ/mol
The G of the combined reaction is the sum of free energy changes of its individual components, so
the coupled reaction is energetically favorable and will proceed as described. Thus, the
energetically unfavorable conversion of A to B is driven by coupling to a second reaction which is
accompanied by a large decrease in free energy. Enzymes are responsible for the coordinated
execution of such coupled reactions.
The cell uses this fundamental mechanism to drive many energetically unfavorable reactions that
must take place in biological systems. Adenosine-5-triphosphate (ATP) plays a central role in this
process by playing a role as a store of free energy inside the cell.
Conclusion
In the above sections the reaction can be interpreted in the broadest possible sense as any change of
matter from one form to another. In addition to these chemical reactions, a reaction can be as simple
as ice (reactants) turning to liquid water (products), the nuclear reactions which take place in the
interior of stars, or elementary particle reactions in the early universe. It doesn’t matter what is the
process, the direction of spontaneous change (at constant temperature and pressure) is always in the
direction of decreasing free energy.Many reactions in the body should be spontaneous in order for
cells to function. Whereas there are some non spontaneous reactions in our body for that we are able
to couple them to thermodynamically favorable (exergonic) reactions that allows the cell to perform
even more complex functions.
 In thermodynamics, entropy (S) refers to the degree of disorder within
a system, while Gibbs free energy (G) is a thermodynamic potential
that combines enthalpy (H) and entropy to determine whether a
process will occur spontaneously at a constant temperature and
pressure; a negative change in Gibbs free energy (ΔG) indicates a
spontaneous process, while a positive ΔG indicates a non-spontaneous
process; "spontaneity" refers to the tendency of a process to occur
naturally without external intervention, and standard free energy
change (ΔG°) is the change in Gibbs free energy when reactants in
their standard states are converted to products in their standard
states.

Key points about entropy and Gibbs free energy:

 Entropy (S):

 A measure of disorder or randomness in a system.

 Generally, processes that increase the entropy of the universe tend to occur
spontaneously.

 The second law of thermodynamics states that the entropy of an isolated

system never decreases.

 Gibbs free energy (G):

 Defined as G = H - TS, where H is enthalpy, T is temperature, and S is entropy.

 A negative ΔG indicates a spontaneous process.

 A positive ΔG indicates a non-spontaneous process.

 At equilibrium, ΔG = 0.

 Spontaneity:

 A spontaneous process occurs naturally without external intervention.

 To determine spontaneity, we analyze the change in Gibbs free energy (ΔG).

 Standard free energy change (ΔG°):

 The change in Gibbs free energy when reactants and products are in their
standard states.

 Used to compare the relative spontaneity of different reactions under standard

conditions.

How to use the Gibbs free energy equation:

 Calculate ΔG: ΔG = ΔH - TΔS

 Interpret the result:

 If ΔG is negative, the process is spontaneous.

 If ΔG is positive, the process is non-spontaneous.

 If ΔG is zero, the system is at equilibrium.