Thermodynamics: the branch of physical science that deals

with the relations between heat and other forms of energy

(such as mechanical, electrical, or chemical energy), and, by
extension, of the relationships and inter convertibility of all
forms of energy.
 Chemical Thermodynamics

• Thermodynamics deals with the relationship

between heat and work. Chemical
thermodynamics is the portion of
thermodynamics that pertains to chemical
reactions.
• The System and Surroundings
The boundary between the system and its
surroundings can be as real as the walls of a
beaker that separates a solution from the rest of
the universe.
• The First Law Of Thermodynamics
The first law of thermodynamics states that the
energy of the universe is constant. Energy can
be transferred from the system to its
surroundings, or vice versa, but it can't be
created or destroyed.

First Law of ΔEuniv = ΔEsys +

Thermodynamics: ΔEsurr
• A more useful form of the first law describes
how energy is conserved. It says that the
change in the internal energy of a system is
equal to the sum of the heat gained or lost by
the system and the work done by or on the
system.
First Law of
ΔEsys = q + w
Thermodynamics:
 Sign convention (related to E)
• The sign convention for the relationship between the internal
energy of a system and the heat gained or lost by the system
can be understood by thinking about a beaker of water
on a hot plate. When the hot plate is turned on,
the system gains heat from its surroundings. As a
result, both the temperature and the internal
energy of the system increase, and Δ E is
positive. When the hot plate is turned off, the water loses
heat to its surroundings as it cools to room temperature, and
Δ E is negative.
• The heat is being exchanged with the surrounding, as total
energy is conserved
 Sign convention (related to q and w)
• The sign conventions for heat, work, and internal energy:
The internal energy and temperature of a system decrease (Δ E <
0) when the system either loses heat or does work on its
surroundings.
Conversely, the internal energy and temperature increase (Δ E >
0) when the system gains heat from its surroundings or when
the surroundings do work on the system.
 Work done During Reaction

• The system is usually defined as the chemical reaction and

the boundary is the container in which the reaction is run.
Esys = q + w
• In thermodynamics, work (W) is defined as the process of
an energy transfer from one system to another.
• In reaction, we can define the amount of work of expansion
done by the reaction is equal to the product of the pressure
against which the system expands times the change in the
volume of the system. REMEMBER it is the change in
volume
w=-PΔV
• The sign convention for this equation reflects the fact that the internal energy of the system decreases when the
system does work on its surroundings.
 w= PΔV

• w = Force * distance
• In an experiment of chemical reaction (a container with
piston) -
• Piston will move if the system works on it
Pressure exerted by the system on the surface of piston
Pressure by the system = Force/Area
Force= P * Area
Therefore, w =P * Area * the distance the piston has moved (
let’s say x)
X= P * A * x
W= P* Δ V
Δ V implies the change in volume that happened
 Internal Energy

• One of the thermodynamic properties of a

system is its internal energy, E
• E is the sum of all sort of energies (kinetic and
potential) of the particles that form the
system.
Ideal Gas-No potential energy but kinetic energy
• The internal energy of an ideal gas is directly
proportional to the temperature of the gas.
Esys = 3/2 RT
R is the ideal gas constant in joules per mole
kelvin (J/mol-K) and T is the temperature in
kelvin.
• The internal energy of systems that are more complex
than an ideal gas can't be measured directly.
• The internal energy of the system is still
proportional to its temperature. We can
therefore monitor changes in the internal
energy of a system by watching what happens to
the temperature of the system. Whenever the
temperature of the system increases we can
conclude that the internal energy of the
system has also increased.
A thermometer immersed in a beaker of water on a hot plate reads
73.5oC can only describe the state of the system at that moment in
time. It can't tell us whether the water was heated directly from
room temperature to 73.5oC or heated from room temperature to
100oC and then allowed to cool.
• Temperature is therefore a state function. It
depends only on the state of the system at any moment
in time, not the path used to get the system to that state.
Because the internal energy of the system is
proportional to its temperature, internal
energy is also a state function. Any change in the
internal energy of the system is equal to the difference
between its initial and final values.
ΔEsys = Ef - Ei
 Enthalpy Versus Internal Energy

• What would happen if we created a set of conditions under

which no work is done by the system on its
surroundings, or vice versa, during a chemical reaction?
Under these conditions, the heat given off or
absorbed by the reaction would be equal to
the change in the internal energy of the
system.
Δ Esys = q (if and only if w = 0)
• The easiest way to achieve these conditions is
to run the
reaction at constant volume, where no work of
expansion is possible. At constant volume, the
heat given off or absorbed by the reaction is
equal to the change in the internal energy that
occurs during the reaction.
Δ Esys = qv (at constant volume)

In a calorimeter reactions can be run at

constant volume.
Ex-reactions, are run in open flasks and beakers. When this is
done, the volume of the system is not constant
because gas can either enter or leave the
container during the reaction. The system is at
constant pressure, however, because the total
pressure inside the container is always equal to
atmospheric pressure.
• If a gas is driven out of the flask during the
reaction, the system does work on its
surroundings. If the reaction pulls a gas into the
flask, the surroundings do work on the system.
We can still measure the amount of heat given off
or absorbed during the reaction, but it is no
longer equal to the change in the internal energy
of the system, because some of the heat has been
converted into work as
Δ Esys = q + w
 Enthalpy
• For a reaction that occurs at constant
pressure, the term enthalpy is used, which is
the sum of the energy of all the atoms and
molecules plus the work of displacing the
environment, that is, the PV work:
H = E + PV
• Thus, the enthalpy change for a chemical
reaction at constant pressure is defined by
the
following equation: ΔHrxn = ΔErxn+ PΔV
• In the case of an enthalpy change which takes
place at 1 atm of pressure, we use the
notation ΔH°rxn.
• Assuming that the only work done by the
reaction is work of expansion gives an
equation in which the PV terms cancel.
Δ H = (qp - PΔV) + PΔV
• Thus, the heat given off or absorbed during a
chemical reaction at constant pressure is
equal to the change in the enthalpy of the
system.
Δ H = qp (at constant pressure)
The relationship between the change in the internal
energy of the system during a chemical reaction and
the enthalpy of reaction can be summarized as
follows-

1. The heat given off or absorbed when a reaction

is run at constant volume is equal to the change
in the internal energy of the system
Δ Esys = qv
2. The heat given off or absorbed when a reaction is
run at constant pressure is equal to the change in
the enthalpy of the system.
Δ Hsys = qp
3. The change in the enthalpy of the system during a
chemical reaction is equal to the change in the
internal energy plus the change in the product of
the pressure of the gas in the system and its volume.
Δ Hsys = Δ Esys + Δ(PV)
 Direction for change
The first law allows us to convert heat into
work, or work into heat. It also allows us to
change the internal energy of a system by
transferring either heat or work between the
system and its surroundings. But it doesn't tell
us whether one of these changes is more easy
to achieve than another.
• Ex-Let’s consider a hot frying pan that has just been removed from the stove
is allowed to come into contact with a cooler object, such as cold water in a
sink, heat will flow from the hotter object to the cooler one, in this case
usually releasing steam. Eventually both objects will reach the same
temperature, at a value between the initial temperatures of the two objects.
This transfer of heat from a hot object to a cooler one obeys the first law of
thermodynamics: energy is conserved.
• Now consider the same process in reverse. Suppose that a hot frying pan in a
sink of cold water were to become hotter while the water became cooler. As
long as the same amount of thermal energy was gained by the frying pan and
lost by the water, the first law of thermodynamics would be satisfied. Yet we
all know that such a process cannot occur: heat always flows from a hot
object to a cold one, never in the reverse direction. That is, by itself the
magnitude of the heat flow associated with a process does not predict
whether the process will occur spontaneously.

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mical_Thermodynamics/19.2%3A_Entropy_and_the_Second_Law_of_Thermodynamics
Therefore, our experiences, tell us that there is a
preferred direction to many natural processes.
Like- a cup of coffee gradually loses heat to its
surroundings as it cools, or when the ice in a glass of
lemonade absorbs heat as it melts. Instead We
would be surprised if a cup of coffee suddenly grew
hotter until it boiled or the water in a glass of
lemonade froze on a hot summer day, even though
neither process violates the first law of
thermodynamics.
Many chemical and physical processes are
reversible and yet tend to proceed in a direction
in which they are said to be spontaneous. This
raises an obvious question: What makes a
reaction spontaneous? What drives the
reaction in one direction and not the other?
So many spontaneous reactions are exothermic that
it is tempting to assume that one of the driving
forces that determines whether a reaction is
spontaneous is a tendency to give off energy.
BUT
There are also spontaneous reactions, however, that
absorb energy from their surroundings. At 100oC,
water boils spontaneously even though the reaction
is endothermic.
H2O(l) → H2O(g) ΔHo = 40.88 kJ/mol
• Thus, the tendency of a spontaneous reaction
to give off energy can't be the only driving
force behind a chemical reaction. There must
be another factor that helps determine
whether a reaction is spontaneous. This
factor, known as entropy, is a measure of the
disorder of the system.
 Entropy and the Second Law of
Thermodynamics
• The second law of thermodynamics describes the
relationship between entropy and the spontaneity of
natural processes.
• Second Law: In an isolated system, natural processes
are spontaneous when they lead to an increase in
disorder, or entropy.
• This statement is restricted to isolated systems to
avoid having to worry about whether the reaction is
exothermic or endothermic. By definition, neither heat
nor work can be transferred between an isolated
system and its surroundings.
• We can apply the second law of
thermodynamics to chemical reactions by
noting that the entropy of a system is a state
function that is directly proportional to the
disorder of the system.
• ΔSsys > 0 implies that the system becomes
more disordered during the reaction.
• ΔSsys < 0 implies that the system becomes
less disordered during the reaction.
• For an isolated system, any process that leads
to an increase in the disorder of the system
will be spontaneous. The following
generalizations can help us decide when a
chemical reaction leads to an increase in the
disorder of the system.
• Solids have a much more regular structure than
liquids. Liquids are therefore more disordered
than solids.
• The particles in a gas are in a state of constant,
random motion. Gases are therefore more
disordered than the corresponding liquids.
• Any process that increases the number of
particles in the system increases the amount of
disorder.
 How H and S affect direction of
reaction
• The sign of ΔH for a chemical reaction affects
the direction in which the reaction occurs.
Spontaneous reactions often, but not always,
give off energy.
• The sign of Δ S for a reaction can also
determine the direction of the reaction.
In an isolated system, chemical reactions occur
in the direction that leads to an increase in the
disorder of the system.
• In order to decide whether a reaction is
spontaneous, it is therefore important to
consider the effect of changes in both
enthalpy and entropy that occur during the
reaction.
 The Third Law of Thermodynamics

• The third law of thermodynamics defines

absolute zero on the entropy scale.
• Third law: The entropy of a perfect crystal is
zero when the temperature of the crystal is
equal to absolute zero (0 K).
• The crystal must be perfect, or else there will
be some inherent disorder. It also must be at
0 K; otherwise there will be thermal motion
within the crystal, which leads to disorder.
• As the crystal warms to temperatures above 0 K, the
particles in the crystal start to move, generating some
disorder. The entropy of the crystal gradually increases
with temperature as the average kinetic energy of the
particles increases.
• At the melting point, the entropy of the system increases
abruptly as the compound is transformed into a liquid,
which is not as well ordered as the solid.
• The entropy of the liquid gradually increases as the liquid
becomes warmer because of the increase in the vibrational,
rotational, and translational motion of the particles. At the
boiling point, there is another abrupt increase in the
entropy of the substance as it is transformed into a
random, chaotic gas.
• The table below provides an example of the
difference between the entropy of a
substance in the solid, liquid, and gaseous
phases.
The Entropy of Solid, Liquid, and Gaseous
Forms of Sulfur Trioxide
Standard-State Entropies of Reaction

• Because entropy is a state function, the change in the

entropy of the system that accompanies any process can be
calculated by subtracting the initial value of the entropy of
the system from the final value.
Δ S = S f - Si
• S for a chemical reaction is therefore equal to the
difference between the sum of the entropies of the
reactants and the products of the reaction.
Δ S = Σ S(products) - Σ S(reactants)
• When this difference is measured under standard-state
conditions, the result is the standard-state entropy of
reaction, Δ So.
• Δ So = Σ So(products) - Σ So (reactants)
• By convention, the standard state for
thermodynamic measurements is characterized
by the following conditions.
Standard-state conditions:
• All solutions have concentrations of 1 M.
• All gases have partial pressures of 0.1 MPa
(0.9869 atm)
• Although standard-state entropies can be
measured at any temperature, they are often
measured at 25oC.
 The Difference Between Enthalpy of
Reaction and Entropy of Reaction
Calculations
• At first glance, tables of thermodynamic data
seem inconsistent. Consider the data in the
table below, for example.
• Thermodynamic Data for Aluminum and Its
Compounds
 The Difference Between Enthalpy of
Reaction and Entropy of Reaction
Calculations
• At first glance, tables of thermodynamic data
seem inconsistent. Consider the data in the
table below, for example.
• Thermodynamic Data for Aluminum and Its
Compounds

Why are they

different?
• For any substance at any particular temperature, we define
the standard enthalpy of formation as the enthalpy change
for a reaction in which the product is one mole of the
substance and the reactants are the compound’s constituent
elements in their standard states (the state g/l/s in which it
is stable at that temperature, this is because the temp. is not
specified at the standard-condition).
• For water at –10°C, this reaction is H2(g,−10°C, 1 bar)+ 12
O2(g,−10°C, 1 bar) →H2O(s,−10°C, 1 bar)
• For water at +10°C, it is H2(g,+10°C, 1 bar)+ 12 O2(g,+10°C, 1
bar) →H2O(liq,+10 ° C, 1 bar)
• For water at +110 ° C, it is H2(g,+110 ° C, 1 bar)+ 12 O2(g,+110
° C, 1 bar) →H2O(g,+110 ° C, 1 bar)
• .
• The standard enthalpy of formation is given the symbol ΔHfo , where the superscript degree sign
indicates that the reactants and products are all in their standard states.
• The subscript, f , indicates that the enthalpy change is for the formation of the indicated
compound from its elements. Frequently, the compound and other conditions are specified in
parentheses following the symbol.
• The solid, liquid, and gas states are usually indicated by the letters “s”, “ ℓ ” (or “liq”), and “g”,
respectively. The letter “c” is sometimes used to indicate that the substance is in a crystalline
state. In this context, specification of the gas state normally means the ideal gas standard state.

• Thermochemical-data tables that include standard enthalpies of formation can be found in a

number of publications or on the internet. For some substances, values are available at a
number of temperatures. For substances for which less data is available, these tables usually give
the value of the standard enthalpy of formation at 298.15 K. (In this context, 298.15 K is
frequently abbreviated to 298 K.)

• For any element at any particular temperature, we define the standard enthalpy of formation to
be zero. When we define standard enthalpies of formation, we choose the elements in their
standard states as a common reference state for the enthalpies of all substances at a given
temperature. While we could choose any arbitrary value for the enthalpy of an element in its
standard state, choosing it to be zero is particularly convenient
• The enthalpy data are given in terms of the
standard-state enthalpy of formation of each
substance, Δ Hfo.
• This quantity is the heat given off or absorbed
when the substance is made from its elements in
their most thermodynamically stable state at
0.1 Mpa (1 bar).
• The enthalpy of formation of AlCl3, for example, is
the heat given off in the following reaction.
standard conditions:
• 1 atm for all gases and a concentration of 1.0 M (1 mol/L) for all species in
solution.
• Each pure substance must be in its standard state, which is usually its most
stable form at a pressure of 1 atm at a specified temperature.
• Enthalpies of formation measured under these conditions are
called standard enthalpies of formation (ΔHof)
• The enthalpy change for the formation of 1 mol of a compound from its
component elements when the component elements are each in their
standard states.
• The standard enthalpy of formation of any element in its most stable
form is zero by definition. (which is pronounced “delta H eff naught”).
• The standard enthalpy of formation of any element in its standard state is
zero by definition.
Example-oxygen can exist as ozone (O3), atomic oxygen (O), and molecular oxygen (O2), O2 is
the most stable form at 1 atm pressure and 25°C. Similarly, hydrogen is H 2(g), not atomic
hydrogen (H). Graphite and diamond are both forms of elemental carbon, but because graphite
is more stable at 1 atm pressure and 25°C, the standard state of carbon is graphite .
Therefore, O2(g), H2(g), and graphite have ΔHof values of zero.

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s_of_Formation
 • The standard enthalpy of formation, ∆Hfo, is the
change
in enthalpy when one mole of a substance is formed
from its elements under a standard pressure of 1
atm.
• The heat of formation of any element in its
standard state is defined as zero.
• The standard enthalpy of reaction, ∆Hfo, is the
sum of the enthalpy of the products minus the
sum of the enthalpy of the reactants.
• ∆Hfo =
• The enthalpy data in this table are therefore relative
numbers, which compare each compound with its
elements.
• Enthalpy data are listed as relative measurements
because there is no absolute zero on the enthalpy
scale. All we can measure is the heat given off or
absorbed by a reaction. Thus, all we can determine is
the difference between the enthalpies of the
reactants and the products of a reaction. We
therefore define the enthalpy of formation of the
elements in their most thermodynamically stable
states as zero and report all compounds as either
more or less stable than their elements.
• Between Graphite and Diamond Which form
of carbon will be considered for standard
enthalpy of formation????

Elements in their standard state are not

formed, they just are
 Hess' Law
• In accordance with Hess' Law, enthalpy
changes for chemical reactions are additive.
• If two chemical equations are added together
to form a third equation, the enthalpy change
of the third equation, ΔH°rxn(3), is equal to
the sum of ΔH°rxn(1) and ΔH°rxn(2).
One way to report the heat absorbed or released would be to compile a massive
set of reference tables that list the enthalpy changes for all possible chemical
reactions, which would require an incredible amount of effort. Fortunately,
Hess’s law allows us to calculate the enthalpy change for virtually any
conceivable chemical reaction using a relatively small set of tabulated data
starting from the elemental forms of each atom at 25 oC and 1 atm pressure.
 Hess' Law
• When applying Hess' law, it is important to
establish a convention for the signs, positive
or negative, of the enthalpy changes. An
exothermic reaction is one which releases
energy and is assigned a negative value. An
endothermic reaction is one which absorbs
energy and is assigned a positive value.
• Coupled Equations: A balanced chemical equation usually does not describe how a reaction occurs, that is, its
mechanism, but simply the number of reactants in products that are required for mass to be conserved. In reality, a
chemical equation can occur in many steps with the products of an earlier step being consumed in a later step. For
example, consider the following reaction phosphorous reacts with oxygen to from diphosphorous pentoxide (2P2O5)
P4+5O2→2P2O5…..(1)

and then the product of that reaction in turn reacts with water to form phosphorus acid

2P2O5+6H2O→4H3PO4……..(2)
In the above equation the P2O5 is an intermediate, and if we add the two equations the intermediate can cancel
out. Hess's law states that if two reactions can be added into a third, the energy of the third is the sum of the energy
of the reactions that were combined to create the third.

• equation 1: P4+5O2→2P2O5………..ΔH1
• equation 2: 2P2O5+6H2O→4H3PO4………….ΔH2
• equation 3 (equation 1 + equation 2): P4+5O2+6H2O→3H3PO4………….ΔH3

Enthalpy is a state function which means the energy change between two states is independent of the path. Since
equation 1 and 2 add to become equation 3, we can say:

• ΔH3=ΔH1+ΔH2(4)
• Hess's Law says that if equations can be combined to form another equation, the enthalpy of reaction of the
resulting equation is the sum of the enthalpies of all the equations that combined to produce it.

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actions/5.7%3A_Enthalpy_Calculations
The additive property of ΔH°rxn values will be applied in this experiment in order to
determine the enthalpy change associated with the
burning of magnesium metal in air.
• For the combustion of magnesium, reaction (1) one possible set of
reactions is:
(2) Mg(s) + 2 H+(aq) → Mg2+(aq) + H2(g) ΔH°rxn(2) = negative
number
(3) MgO(s) + 2 H+(aq) → Mg2+(aq) + H2O (l) ΔH°rxn(3) = negative
number
(4) 1/2 O2 (g) + H2(g) → H2O (l) ΔH°rxn(4) = negative number

• Reaction (1)- (1) Mg(s) + 1/2 O2(g) → MgO(s) is equal to reaction

(2) minus reaction (3) plus reaction (4):
• ΔH°rxn(1) = ΔH°rxn(2) – ΔH°rxn(3) + ΔH°rxn(4)
• The enthalpy of formation of liquid H2O has been
measured and is given by:
ΔH°rxn(4) = ΔH°f (H2O) = –285840 Joules/mole =
–285.84 kJ/mol
• The enthalpies of reactions (2) and (3) are
measurable quantities. Heat is released by the
addition of excess strong acid to Mg, thus the
quantity ΔH°rxn(2) will be a negative number.
Similarly, the addition of excess strong acid MgO
will release heat, and ΔH°rxn(3) will also be
negative.
• Entropy data are different. The third law
defines absolute zero on the entropy scale. As
a result, the absolute entropy of any element
or compound can be measured by comparing
it with a perfect crystal at absolute zero. The
entropy data are therefore given as absolute
numbers, So, not entropies of formation,
ΔSof.
Driving Forces and Gibbs Free Energy

• Some reactions are spontaneous because

they give off energy in the form of heat ( ΔH <
0). Others are spontaneous because they lead
to an increase in the disorder of the system
(Δ S > 0). Calculations of Δ H and ΔS can be
used to probe the driving force behind a
particular reaction.
• What happens when one of the potential
driving forces behind a chemical reaction is
favorable and the other is not? We can
answer this question by defining a new
quantity known as the Gibbs free energy (G)
of the system, which reflects the balance
between these forces.
• The Gibbs free energy of a system at any
moment in time is defined as the enthalpy of
the system minus the product of the
temperature times the entropy of the
system.
G = H - TS
• The Gibbs free energy of the system is a state
function because it is defined in terms of
thermodynamic properties that are state
functions. The change in the Gibbs free energy of
the system that occurs during a reaction is
therefore equal to the change in the enthalpy of
the system minus the change in the product of the
temperature times the entropy of the system.
ΔG = Δ H - TΔS
• As we have seen, the enthalpy and entropy
terms have different sign conventions.
• The entropy term is therefore subtracted from
the enthalpy term when calculating Δ Go for a
reaction.
• Because of the way the free energy of the system
is defined, Δ G is negative for any reaction for
which Δ H is negative and Δ S is positive. Δ G is
therefore negative for any reaction that is favored
by both the enthalpy and entropy terms. We can
therefore conclude that any reaction for which Δ
G is negative should be favorable, or
spontaneous.
• Favorable, or spontaneous reactions:
ΔG<0
• Conversely, ΔG is positive for any reaction for
which ΔH is positive and ΔS is negative. Any
reaction for which ΔG is positive is therefore
unfavorable.

Unfavorable, or
ΔG > 0
non-spontaneous reactions:
• Reactions are classified as either exothermic (
ΔH < 0) or endothermic (Δ H > 0) on the basis
of whether they give off or absorb heat.
Reactions can also be classified as exergonic
(Δ G < 0) or endergonic (Δ G > 0) on the basis
of whether the free energy of the system
decreases or increases during the reaction.
• When a reaction is favored by both enthalpy
(Δ H < 0) and entropy (Δ S > 0), there is no
need to calculate the value of Δ G to decide
whether the reaction should proceed. The
same can be said for reactions favored by
neither enthalpy (Δ H > 0) nor entropy (Δ S <
0). Free energy calculations become important
for reactions favored by only one of these
factors.
• The beauty of the equation defining the free
energy of a system is its ability to determine
the relative importance of the enthalpy and
entropy terms as driving forces behind a
particular reaction. The change in the free
energy of the system that occurs during a
reaction measures the balance between the
two driving forces that determine whether a
reaction is spontaneous.
• If the reaction is run at constant temperature,
this equation can be written as follows.
ΔG = Δ H - T Δ S
• The change in the free energy of a system that
occurs during a reaction can be measured under
any set of conditions. If the data are collected
under standard-state conditions, the result is the
standard-state free energy of reaction (ΔGo).
ΔGo = Δ Ho - TΔ So
• What is the standard free-energy change (ΔG°)?
- is the change in free energy when one substance or a set of substances in their
standard states (the state g/l/s in which they are stable at standard condition; temp. not
specified at standard condition)is converted to one or more other substances, also in their
standard states.

• What is the standard free-energy of formation (ΔG°f)?

The standard free energy of formation (ΔG° f)of a compound is the change in free energy that
occurs when 1 mol of a substance is formed from the component elements in their
standard states.
By definition, the standard free energy of formation of an element in its standard
state is zero at 298.15 K.
Tabulated values of standard free energies of formation allow chemists to calculate the values of ΔG° for a wide variety of
chemical reactions rather than having to measure them in the laboratory.

• What does Gibb’s free energy of formation tell us?

The sign of ΔG indicates the direction of a chemical reaction and determines if a reaction is spontaneous or not.

Source:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_General_Chemistry_(Petrucci_et_al.)/19%3A_Spontaneous_Ch
ange%3A_Entropy_and_Gibbs_Energy/19.6%3A_Gibbs_Energy_Change_and_Equilibrium
• standard states (the state g/l/s in which it is stable at 0.1
Mpa/1 M concentration, temp. not specified at standard
condition).
• For water at –10°C, this reaction is H2(g,−10°C, 1 bar)+ 12
O2(g,−10°C, 1 bar) →H2O(s,−10°C, 1 bar)
• For water at +10°C, it is H2(g,+10°C, 1 bar)+ 12 O2(g,+10°C, 1
bar) →H2O(liq,+10 ° C, 1 bar)
• For water at +110 ° C, it is H2(g,+110 ° C, 1 bar)+ 12 O2(g,+110
° C, 1 bar) →H2O(g,+110 ° C, 1 bar)
• .
The Effect of Temperature on the Free
Energy of a Reaction
• The balance between the contributions from the
enthalpy and entropy terms to the free energy of a
reaction depends on the temperature at which the
reaction is run.
• The equation used to define free energy suggests that
the entropy term will become more important as the
temperature changes.
» ΔGo = Δ Ho - T Δ So
 • The relationship between the free energy of reaction at any
moment in time (ΔG) and the standard-state free energy of
reaction (ΔGo) is described by the following equation.
ΔG = ΔGo + RT ln Q
In this equation, R is the ideal gas constant in units of J/mol-K,
T is the temperature in kelvin, ln represents a logarithm to the
base e, and Q is the reaction quotient at that moment in time.
• As we have seen, the driving force behind a chemical
reaction is zero (ΔG = 0) when the reaction is at
equilibrium (Q = K).
0 = ΔGo + RT ln K
• We can therefore solve this equation for the relationship
between ΔGo and K.
ΔGo = - RT ln K
This equation allows us to calculate the equilibrium constant
for any reaction from the standard-state free energy of
reaction, or vice versa.

• The key to understanding the relationship between ΔGo and

K is recognizing that the magnitude of ΔGo tells us how far
the standard-state is from equilibrium. The smaller the
value of ΔGo, the closer the standard-state is to
equilibrium (ΔG=0). The larger the value of ΔGo, the
further the reaction has to go to reach equilibrium.
• The equilibrium constant for a reaction can be
expressed in two ways: Kc and Kp. We can write
equilibrium constant expressions in terms of the
partial pressures of the reactants and products, or in
terms of their concentrations in units of moles per
liter.

• For gas-phase reactions the equilibrium constant

obtained from ΔGo is based on the partial pressures of
the gases (Kp). For reactions in solution, the
equilibrium constant that comes from the calculation
is based on concentrations (Kc).
 The Temperature Dependence of
Equilibrium Constants
• Equilibrium constants are not strictly constant
because they change with temperature. We are now
ready to understand why.
• The standard-state free energy of reaction is a
measure of how far the standard-state is from
equilibrium.
ΔGo = - RT ln K
But the magnitude of ΔGo depends on the temperature
of the reaction.
ΔGo = ΔHo - T ΔSo
As a result, the equilibrium constant must depend on
the temperature of the reaction.
 The Relationship between ΔG⁰ and K

• There is a direct relationship between ΔG⁰ and the equilibrium constant K.

We can establish this relationship by substituting the equilibrium values
(ΔG = 0, and K = Q) into the equation for determining free energy change
under nonstandard conditions:

• ΔG = ΔG⁰ + RT ln Q

0 = ΔG⁰ + RT ln K (at equilibrium)

ΔG⁰ = – RT ln K
We now have a way of relating the equilibrium constant directly to
changes in enthalpy and entropy. As well, we can now determine the
equilibrium constant from thermochemical data tables or determine the
standard free energy change from equilibrium constants.

REMEMBER K IS NOT NECESSARILY EQUAL TO 1 IN EQUILIBRIUM

SOURCE: https://opentextbc.ca/introductorychemistry/chapter/free-energy-under-nonstandard-conditions-2/
The relationship between ΔGo and the equilibrium constant for a
chemical reaction is illustrated by the data in the table below.
Values of ΔGo and K for Common Reactions at 25oC
The Relationship Between Free Energy
and Equilibrium Constants
• The difference between ΔGo and Δ G for a
reaction is important. There is only one value of Δ
Go for a reaction at a given temperature, but
there are an infinite number of possible values of
Δ G.
• The figure below shows the relationship between
Δ G for the following reaction and the logarithm
to the base e of the reaction quotient for the
reaction between N2 and H2 to form NH3.
N2(g) + 3 H2(g) ↔2 NH3(g)
 Interpreting Standard-State Free
Energy of Reaction Data
• What does the value of ΔGo tell us about the
following reaction?
N2(g) + 3 H2(g) ↔ 2 NH3(g) ΔGo = -32.96 kJ at 25°C
But at 500 °C ΔGo =61.4 KJ
By definition, the value of ΔGo for a reaction measures the
difference between the free energies of the reactants and
products when all components of the reaction are present
at standard-state conditions.
At which temperature the forward reaction is favourable?
• The sign of ΔGo tells us the direction in which the
reaction has to shift to come to equilibrium.
• The fact that ΔGo is negative for this reaction at 25oC
means that a system under standard-state conditions
at this temperature would have to shift to the right,
converting some of the reactants into products, before
it can reach equilibrium. The magnitude of ΔGo for a
reaction tells us how far the standard state is from
equilibrium. The larger the value of ΔGo , the further
the reaction has to go to get to from the
standard-state conditions to equilibrium.
• Assume, for example, that we start with the following
reaction under standard-state conditions, as shown in
the figure below.
• N2(g) + 3 H2(g) ↔ 2 NH3(g)
• At 25°C ∆Go therefore
describes this reaction
only when
all three components
are present at 1 atm pressure
(as the reactant-product are in
standard state)
 Standard-State Free Energy of
Reaction
• The value of ΔG at that moment in time will be equal
to the standard-state free energy for this reaction,
ΔGo.
When Q = 1 (measured from partial pressure)
Δ G = Δ Go (ΔG = ΔG⁰ + RT ln Q)
• As the reaction gradually shifts to the right, converting
N2 and H2 into NH3, the value of Δ G for the reaction
will decrease. If we could find some way to harness
the tendency of this reaction to come to equilibrium,
we could get the reaction to do work. The free energy
of a reaction at any moment in time is therefore said
to be a measure of the energy available to do work.
 Data on the left side of this figure
correspond to relatively small
values of Q. They therefore
describe systems in which there is
far more reactant than product.
The sign of ΔG for these systems is
negative and the magnitude of Δ G
is large. The system is therefore
relatively far from equilibrium and
the reaction must shift to the right
Q=partial P of
to reach equilibrium.
Pr/ partial P of
Re
 Data on the far right side of this
figure describe systems in which
there is more product than
reactant. The sign of ΔG is now
positive and the magnitude of Δ G
is moderately large. The sign of Δ G
tells us that the reaction would
have to shift to the left to reach
equilibrium. The magnitude of Δ G
tells us that we don't have quite as
Q=partial P of
far to go to reach equilibrium.
Pr/ partial P of
Re
 The points at which the straight line
in the above figure cross the
horizontal and vertical axes of this
diagram are particularly important.
The straight line crosses the vertical
axis when the reaction quotient for
the system is equal to 1 (as the
example is gas, so all at 1
atmosphere at standard condition
and 25°C, we will consider partial
pressure). This point therefore
describes the standard-state
conditions, and the value of ΔG at
When QP= 1: Δ G= this point is equal to the
ΔGo standard-state free energy of
reaction, Δ Go.
 The point at which the straight line
crosses the horizontal axis
describes a system for which ΔG is
equal to zero. Because there is no
driving force behind the reaction,
the system must be at equilibrium.

When Qp = Kp: ΔG = 0
• http://chemed.chem.purdue.edu/genchem/to
picreview/bp/ch21/entropy.php
 Some definitions

▪ A system is some part of the universe that you want to study

and understand
• The surroundings are everything else in the universe that is not
in our system
• The system can be open or closed to (isolated from) the
surroundings in terms of both matter and energy

Natural systems tend toward states of

minimum energy
 • Open System:
It is a system in which both mass interaction as well as energy
interaction takes place.
Ex: Water flowing in a pipeline line.{Mass and K.E of water}
Closed System:
It is a system in which there is only energy interaction takes
place but not mass interaction.
Ex: SUN
Isolated Systems:
It is a system in which neither mass interaction nor energy
interaction takes place.
Ex: Coffee in a thermos flask.
 Some definitions

▪ The Phase is any mechanically separable and chemically

homogenous portion of the system

▪ Component is minimum number of constituents required to

describe system.
 Some definitions

• In our case, a system is likely to be a mineral or a rock

•A phase is any mechanically separable and chemically
homogenous portion of the system, e.g. a melt, a fluid,
or a mineral in a rock
•In this case, it is comprised of chemical components
that describe chemical variability in that mineral or a
rock
• A reaction is anything that changes the nature of the
phases within a system
 Some definitions

• Thermodynamics is primarily concerned with

macroscopic energies of microscopic processes that we
might or might not fully understand.
• It is convenient to group all of the variables required
into two classes:
Intensive variables are independent of the amount
of material present:
e.g. Pressure (P) & Temperature (T)
Extensive variables are dependent on the amount
of material present:
e.g. Volume (V) & Entropy (S)
The First Law of Thermodynamics states that "the internal energy, E, of an
isolated system is constant".

In a closed system, there cannot be a loss or gain of mass, but there can be a
change in energy, dE.

dE = dQ - dW (1)

Q=heat
W=work done by the system

W=force x distance.
Pressure, P= Force/surface area,
Force = P x surface area,

Therefore, W = P x surface area x distance = P x V

V is volume.
If the work is done at constant pressure, then dW = PdV. Substitution of this
relationship into (1) yields:
dE = dQ - PdV (2)
This is a restatement of the first law of thermodynamics.
• The Second Law is concerned with the
maximum fraction of heat that can be
converted into useful work.
• The second law may be stated in several
different ways, such as :
• a) Thermal energy will not spontaneously flow
from a colder to a warmer object.
• b) The entropy (example next slide) of the
universe is constantly increasing.
dS=dQ/T
The Second Law of Thermodynamics states that the
change in heat energy of the system is related to the
amount of disorder in the system. Entropy is a
measure of disorder, and so at constant Temperature
and Pressure:
dq = TdS

Thus, substituting into dE=dQ-PdV we get:

dE = TdS - PdV (3)
The Gibbs Free Energy, G, is defined as the energy in
excess of the internal energy as follows:
G = H-TS=E + PV - TS (4)
Differentiating this we get:
dG = dE +VdP + PdV - TdS - SdT
Substituting (3) into this equation then gives:
dG = TdS - PdV + VdP + PdV - TdS - SdT
or
dG = VdP - SdT (5)
For a system in equilibrium at constant P and T, dG = 0.
If we differentiate equation (5) with respect to P at constant T, the
result is:
(6)

and if we differentiate equation (5) with respect to T at constant P

we get:
(7)

Equation (6) tells us that phases with small volume are favored at
higher pressure, and equation
(7) tells us that phases with high entropy (high disorder) are favored
at higher temperature.
Equation (5), dG = VdP – SdT,
tells us that the Gibbs Free
Energy is a function of P and T.

In the diagram, phase A has a

steeply sloping free energy
surface. Phase B has a more
gently sloping surface.
Where the two surfaces
intersect, Phase A is in
equilibrium with phase B, and
GA = GB
.
At constant P
below TE phase A has the
lowest Gibbs Free Energy, G. At
these
temperatures, phase A is stable
and phase B is not stable
because
it has a higher free energy.
Note that at TE
the free energy of the
phase A and B
are same.
At temperatures greater than T
phase B has a lower free energy
than phase A, and thus phase B
is stable.
Next, we look at a section of G versus P
at constant T.

GA= GB at PE
. At pressures greater than P
phase B is
stable because it has a lower G than
phase A. At pressures less than PE
phase A is stable because it has a
lower G than phase B.
Finally, we look at a cross-section
across the bottom of the first
figure. Here we project the line of
intersection of the Free Energy
surfaces onto the P - T plane. Along
the line of intersection of the
surfaces GA= GB
. The line separates two fields, one
at low P in
which A is the stable phase and one
at higher P in which phase B
B
is stable. This is a classic P-T phase
diagram. The line represents
all values of P and T where
For a reaction, A ↔B
dΔG = ΔVdP - ΔSdT (8)
ΔG = the change in Gibbs Free Energy of the reaction
ΔS = the change in entropy of the reaction
and ΔV = the change in volume of the reaction

ΔS=∑ SPr- ∑ Sre

ΔV= ∑ VPr- ∑ VRe

At equilibrium, as we have just seen, ΔG = 0, so from

equation (8)
0 = ΔVdP - ΔSdT
Rearranging this equation yields

( 9)
This relation is known as the Clausius - Clapeyron
Equation. It is important because it tells us the
slope of the equilibrium boundary or reaction
boundary on a Pressure versus Temperature
phase diagram.

We next look at two cases of chemical reactions.

In the first case, the chemical reaction is
between only solid phases. In the second case a
fluid or gas is involved as one of the products of
the reaction.
Solid - Solid Reactions

Only involves solid phases, with no fluid phases.

Most solid-solid reactions appear as straight lines on P-T diagrams.

Why?????

The reason for this comes from the Clausius-Clapeyron equation.

dP/dT = ΔS/ΔV

As T increases, both S and V increase, disorganized at high

temperature, high entropy, molecule vibrates more, high V

Similarly, V tend to decrease with increasing pressure (less room to

vibrate means better organization and lower volume).

The change in volume and entropy at any given temperature and

pressure tends to be small. A curve whose slope is constant is a
straight line.
Let's use these principles to analyze some solid - solid
reactions,
such as those in the Al2SiO5
phase diagram. Note that for the
solid-solid reaction Andalusite <=> Kyanite, dP/dT is
positive.
This is what we expect, because the product kyanite,
occurs on the low T side of the reaction boundary
Entropy for Ky low or high?
ΔS negative
Increasing the pressure causes a decrease in volume,
Volume for Ky low or high?
ΔV is also negative
With both ΔS and ΔV negative, the slope
of the boundary curve dP/dT is positive.
For the reaction Kyanite <=> Sillimanite,

ΔS is positive.-RIGHT???
ΔV is also positive-?????
is also positive.
Note that the reaction boundary for
Andalusite <=> Sillimanite
has a negative slope.

ΔV is negative or postive?
ΔS s positive or negative?

dP/dT negative.
Devolatization Reactions

Devolatilization reactions appear as curves on Pressure

Temperature
diagrams.
A <=> B + H2O.

For this reaction we can write:

and
ΔS = SB + SH2O- SA
= ΔSsolids+SH2O
ΔV = VB + VH2O- VA
= ΔVsolids+ VH2O
 • VA VB VH2O delta V (VB+ VH2O-VA)
12 7 17 12
11 6 5 0
10 5 3 -2
Increasing temperature will generally cause S
to be positive
especially for this reaction in which a
gas or fluid phase is produced, because gases
always have a higher entropy (randomness)
than ΔS = SB + SH2O- SA
solids. = ΔSsolids+SH2O
ΔV = VB + VH2O- VA
At low pressure ΔV positive. = ΔVsolids+ VH2O
At low pressure fluid or gas will expand to fill
space available

dP/dT will be positive.

As the pressure increases, the fluid or gas will

be more
compressible than the solids, so the total ΔV
will
become increasingly smaller. Thus, dP/dT(=
ΔS/ ΔV) will increase.
G = H – TS is also a very useful relation:
where G is the Gibbs Free Energy, H is the enthalpy, T is the absolute temperature in
Kelvin,
and S is the entropy.
For a chemical reaction, we can rewrite this as:
ΔG = ΔH - TΔS (10)

For a reaction Reactant=Product

ΔG = ∑ GPr- ∑ Gre
ΔS=∑ SPr- ∑ Sre
ΔH= ∑ HPr- ∑ Hre

In general ΔG, ΔH, ΔS, and ΔV are dependent of Pressure and Temperature, but at any
given T & P:
If ΔG < 0 (negative) the chemical reaction will be spontaneous and run to the right,
If ΔG = 0 the reactants are in equilibrium with products,
and if ΔG > 0 (positive) the reaction will run from right to left.
● G is a measure of relative chemical stability for a
phase
● We can determine G for any phase by measuring H
and S for the reaction creating the phase from the
elements
● We can then determine G at any T and P
mathematically
● Most accurate if we know how V and S vary

with P and T
• dV/dP is the coefficient of isothermal
compressibility
• dS/dT is the heat capacity (Cp)
Temperature Dependence of G, H, and S
As stated above, G, H, and S depend on Temperature and Pressure. But,
because G depends on
H and S, it is usually more convenient to consider the temperature dependence
of H and S, so
that if we know H and S at any given temperature, we can calculate G.

where Cp is the heat capacity at constant pressure. The heat capacity is the
amount of heat necessary to raise the temperature of the substance by 1 oK.
CP can be expressed in terms of power series f T
CP=a+bT+c/T2............

(a+bT+c/T2) dT

=a(T2 - T1) + b(T22 - T12)/2 - c/(T2-1 - T1-1)

Tables of thermodynamic data are usually tabulated at some known reference

temperature and pressure, most commonly at a Temperature of 298 K, and
Pressure of 1 bar ( = 0.1 MPa ~ 1atm).
Thus, we if we need to know H at some temperature, T, other than 298 K, we can
use the above equation to determine H at the new temperature:
(T1 is 298K)
 The temperature dependence of entropy, S, is given by:

[(a+bT+c/T2) /T] dT

=a(ln T2 - ln T1) + b(T2 - T1) - c(T2-2

Calculating entropy:
- T1-2)/2
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/DeVoes_Thermodynamics_and_Chemistry/06%3A_The_Third_Law_and_Cry
genics/62_Molar_Entropies
Calculating entropy:
http://www.docbrown.info/page07/delta1Hc.htm
• Determining Enthalpies
Thus, if we want to measure how the internal energy E of a crystal
changes ΔE with increasing temperature at constant pressure, we
want to know Δ H, and we can get that by integrating the heat
capacity CP over the temperature range of interest.
There's another way to measure Δ H, though: calorimetry.

• By dissolving a mineral in acid and measuring the heat produced

by the dissolution, we get a heat of dissolution (usually positive).
The enthalpy of "formation" Δ fH° of the mineral is then just the
opposite of the heat of dissolution (usually negative). Exceptions
to the "usually positive/negative" rule include CN, HCN, Cu2+, Hg2+,
NO, Ag+, and S2-. Enthalpies of formation appear in tables of
thermodynamic data and are usually referenced to 298 K and 1
atm.
Source:
https://www.alevelh2chemistry.com/chemical-energetics-experimental-method-to-determine-
enthalpy-change-of-combustion/#:~:text=Experimental%20Determination%20of%20Enthalpy%
20Change%20of%20Combustion%2C%20%CE%94H&text=The%20heat%20released%20during
%20combustion,of%20the%20water%20to%20rise.
• Enthalpy of Reaction
To get an enthalpy of reaction rH° we can measure the enthalpies
of formation of the reactants and products fH° and then take the
difference between them as Δ rH° = Δ fH°products- Δ fH°reactants
• For example, we can compute the enthalpy of the reaction
anhydrite + water = gypsum:

• CaSO4 + 2H2O = CaSO42H2O

• from Ca + S + 2O2 = CaSO4 Δ fH° = -1434.11 kJ/mol

• H2 + 0.5O2 = H2O Δ fH° = -285.830 kJ/mol
• Ca + S + 3O2 + 2H2 = CaSO42H2O Δ fH° = -2022.63 kJ/mol
• Thus, Δ rH° = Δ fH°gypsum - Δ fH°anhydrite - Δ fH°water = -16.86
kJ/mol.
• Calculating fH° at Temperatures Other Than 298 K
• So far we know how to calculate the change in
enthalpy caused by heating and we know that we can
get enthalpies of formation from tables. What if we
want to know the enthalpy of formation of a mineral
at a temperature other than 298 K?
We do this by calculating ΔrCP for the reaction that
forms the mineral of interest: Δ rCP = Δ rCPproducts - Δ
C
r Preactants
• and then integrating. Thus, for example if we want to
know Δ fH° for quartz at 1000 K, we get coefficients for
the heat capacities of Si, O2 and SiO2:
Enthalpy of formation of quartz at standard conditions (meansured at 298 K and
standard condition)
ΔfH°Qtz (kJ/mol) -910.86
• http://www.geol.ucsb.edu/faculty/hacker/geo
124T/lecture.html
• https://opentextbc.ca/introductorychemistry/
chapter/free-energy-under-nonstandard-cond
itions-2/
 NaAlSi3O8 = NaAlSi2O6 + SiO2
P - T phase diagram of the equilibrium curve
How do you know which side has which phases?

Figure 27.1. Temperature-pressure

phase diagram for the reaction:
Albite = Jadeite + Quartz calculated
using the program TWQ of Berman
(1988, 1990, 1991). Winter (2010)
An Introduction to Igneous and
Metamorphic Petrology. Prentice
Hall.
 pick any two points on the equilibrium curve
dΔG = 0 = ΔVdP - ΔSdT
dP ΔS
Thus =
dT ΔV

Figure 27.1. Temperature-pressure

phase diagram for the reaction:
Albite = Jadeite + Quartz calculated
using the program TWQ of Berman
(1988, 1990, 1991). Winter (2010)
An Introduction to Igneous and
Metamorphic Petrology. Prentice
Hall.
 Gas Phases

Return to dG = VdP - SdT, for an isothermal process:

G P −G P =
2 1 z
P2

P1
VdP

For solids it was fine to ignore V as f(P)

For gases this assumption is not right
You can imagine how a gas compresses as P increases
How can we define the relationship between V and P for a gas?
Gas Pressure-Volume Relationships

Ideal Gas
– As P increases V decreases
– PV=nRT Ideal Gas Law
• P = pressure
• V = volume
• T = temperature
• n = # of moles of gas
• R = gas constant
= 8.3144 J mol-1 K-1
Figure 5.5. Piston-and-cylinder apparatus to
compress a gas. Winter (2010) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.
P x V is a constant at constant T
Gas Pressure-Volume Relationships
Since G P −G P =
2 1 z
P2

P1
VdP

we can substitute RT/P for V (for a single mole of gas), thus:

G P −G P =
2 1 z
P2

P1
RT
P
dP
and, since R and T are certainly independent of P:

G P − G P = RT
2 1 z P2

P1
1
P
dP
Gas Pressure-Volume Relationships
And since z 1
x
dx = ln x

GP2 - GP1 = RT (ln P2 - ln P1 )= RT ln (P2/P1)

Thus the free energy of a gas phase at a specific P and T, when

referenced to a standard state of 0.1 MPa becomes:

GP, T - GT = RTo ln (P/Po)

G of a gas at some P and T = G in the reference state (same T and 0.1 MPa)
+ a pressure term
Gas Pressure-Volume Relationships
The form of this equation is very useful

GP, T - GT = RTo ln (P/Po)

For a non-ideal gas (more geologically appropriate) the same

form is used, but we substitute fugacity ( f ) for P

where f = γP γ is the fugacity coefficient

Tables of fugacity coefficients for common gases are available

At low pressures most gases are ideal, but at high P they are
not
 Chemical potential as a function of
pressure at constant temperature, for a
real gas (solid curve) and the same gas
behaving ideally (dashed curve). Point A
is the gas standard state. Point B is a
state of the real gas at pressure pʹ . The
fugacity f(pʹ) of the real gas at pressure
pʹ is equal to the pressure of the ideal
gas having the same chemical potential
as the real gas (point C).

Fugacity is a kind of effective

pressure. Specifically, it is the
pressure that the hypothetical
ideal gas (the gas with
intermolecular forces “turned
off” ) would need to have in
order for its chemical potential
at the given temperature to be
the same as the chemical
potential of the real gas (see
point C in Fig. 7.6). If the gas
is an ideal gas, its fugacity is
Source: equal to its pressure.
https://chem.libretexts.org/Bookshelves/Physical_and_Theoret
ical_Chemistry_Textbook_Maps/DeVoes_Thermodynamics_and
_Chemistry/07%3A_Pure_Substances_in_Single_Phases/78_Ch
emical_Potential_and_Fugacity

An ideal gas is in its standard state at a given temperature when its

pressure is the standard pressure.
 Dehydration Reactions

• Mu + Q = Kspar + Sillimanite + H2O

• We can treat the solids and gases separately
GP, T - GT = ΔVsolids (P - 0.1) + RT ln (PH2O/0.1) (isothermal)
• The treatment is then quite similar to solid-solid reactions, but
you have to solve for the equilibrium P by iteration
 Considering ideal behaviour of gas phase, we can write for it
PH2O

G=H-TS (In standard state

of the gas)
 Fluid

If PFluid=PLith, then, XH2OPFluid = XH2OP

Dehydration Reactions
(qualitative analysis)
dP = ΔS
dT ΔV

Figure 27.2. Pressure-temperature

phase diagram for the reaction
muscovite + quartz = Al2SiO5 +
K-feldspar + H2O, calculated using
SUPCRT (Helgeson et al., 1978). Winter
(2010) An Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
 As, dG α =∑µidni at constant P, T

GOl=nFoµFo+nFaµFa
If ‘N’=∑n=ni+nj+nk+.....
Gα/N=∑(ni/N)µi
=
∑Xiµi (X=Mole fracion)
Gα/N= Molar Gibb’s free energy
Intensive or extensive variable?
For pure phase Xi=1 as (ni/ni),
Therefore, Molar Gibb’s free energy=µi for
pure phase
Fundamental Equation of Chemical Thermodynamics

Gibbs free energy will be of most interest to us, since P and T are the most obvious
choices of independent variables for geologic application
Open System

Gibbs free energy will be of most interest to us, since P and T are the most obvious
choices of independent variables for geologic application
Close System
 Diffusion
• At equilibrium- µi of component i must be
same in every coexisting phases that contain
it.
• If µi is lower in one phase that the other, free
energy of system could be lowered by
migration of the component from a phase
with higher µi to a phase with lower µi
• Difference in µi drives diffusion.
 Response of system when A
or B atom is introduced-
Calculate the XB and draw a
tangent from the point on
the curve that corresponds
to the specific XB.
The µA and µB are the
corresponding chemical
potential of the A and B
phases.,

P, T constant
 If homogenized mixture has lower energy (X0)
Location 2-
µ A< µ B

Location 1-
µ A> µ B

Therefore between these two Location in a system

A will flow from 1 to 2

And

B will flow from 2 to 1

P, T constant
Till the system become homogenous X0 to minimize
energy.
 If homogenized mixture has higher energy (X0)
Location 2-
µA>µB

Location 1-
µ A< µ B

X0 Therefore between these two Location in a system

B will flow from 1 to 2

And
A will flow from 2 to 1

And finally the system will have two zones (/two p

hases) one corresponding to Xα composition and
another corresponding to Xß, to minimize energy.

P, T constant Lowering of energy leads to phase separation

• Jd+Qtz=Ab
• If pure phases and no solid solution, we can
write
• ΔG=GAb-GQtz-GJd
• Gα/N=∑(ni/N)µi=∑Xiµi,
• Therefore for this equation Gα =µi and we can
write it as ΔG=µPlAb-µQtz-µCpxJd=0 (at eqilibrium)
 Solutions: T-X relationships
Example: orthopyroxenes (Fe, Mg)SiO3
– Real vs. Ideal Solution Models

Figure 27.3. Activity-composition relationships for the enstatite-ferrosilite mixture in orthopyroxene at 600 oC and 800oC. Circles are data
from Saxena and Ghose (1971); curves are model for sites as simple mixtures (from Saxena, 1973) Thermodynamics of Rock-Forming
Crystalline Solutions. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Why activity or fugacity?
 Why activity or fugacity?
There are two ways to deal with real systems that deviate appreciably from
ideal conditions:
1.Use a more accurate phenomenologically (i.e., real) Equation of State like the
van der Waal' that models the system more accurately. This must explicitly
address intermolecular forces and other effects that exist in real system and the
concentration used is 1 mol/L (i.e., the real concentration).

2.Use an ideal equation pf state like the ideal gas Equation of State in, but use an
"effective concentration" of 0.816 mol/L to generate the observed pressure (that
is, the gas behaves as if it has a reduced concentration of 100%-18.36% =
81.6% of the real concentration).
 Why activity or fugacity?
The activity of a substance describes the effective concentration
of that substance in the reaction mixture. Activity takes into
account the non-ideality of the reaction mixture, including
solvent-solvent, solvent-solute, and solute-solute interactions.
Thus, activity provides a more accurate description of how all of
the particles act in solution.

For very dilute solutions, the activities of the substances in the

solution closely approach the formal concentration (what the
calculated concentration should be based on how much substance
was measured out.) As solutions get more concentrated, the
activities of all of the species tend to be smaller than the formal
concentration.
• Activities are actually unitless ratios (concentration
has unit) that compare an effective pressure or an
effective concentration to a standard state pressure
or concentration (the correct term for the effective
pressure is fugacity). There are several ways to
define standard states for the different components
of a solution, but a common system is
• the standard state for gas pressure, P°, is 1 bar (often approximated with
1 atm)
• the standard state for solute concentration, C°, is 1 molal (moles
solute/kg solvent) for dilute solutions. Often molality is approximated
with molarity (moles solute/Liter solution).
• the standard state for a liquid is the pure liquid
• the standard state for a solid is the pure solid
Activity
 Activity
• In reality, no phases behave ideally and we write
µiα - µ°i = RT lnai α
In this equation, μi α is the chemical potential of the
component in a solid solution, μio is the chemical
potential of the component in a pure end-member
(the molar free energy of the pure phase), and ai α is
the activity (effective concentration) of the
component (i) in phase (α).
• For solid: The value of γ depends
on:
a = (γX)Z – Concentration of ions
and charge in the
• For ideal gas: solution
– Charge of the ion
aiα =Pi/Piref – Diameter of the ion

• For real gas:

aiα=fi/firef
• The activity of a component, ai α, is related to
the mole fraction of that component in a solid
phase, Xi α. Activity increases as mole fraction
increases. This relationship applies to solids
and also to components in aqueous solution
or gaseous mixture (partial pressure/fugacity).
• a = (γX)Z
where a = activity of a compound, ‘Z’ is the
"site occupancy coefficient" (e.g., = 2 for Mg in
Mg2SiO4), and γ is the activity coefficient that
describes the non-ideal behavior.
• For ideal solution γ=1. therefore, a=X.
• For pure substance a=1
• In general, a mineral end member exhibits
nearly ideal behavior at very low mole
fractions or very high mole fractions. For such
compositions, activity is approximately equal
to mole fraction. For example, olivine
compositions Fo98Fa02 or Fo02Fa98 have
forsterite activities of about 0.98 and 0.02,
respectively; the activity of forsterite for both
compositions is nearly ~aFo=XFo.
• In general, mineral solid solutions have more
ideal behavior at higher temperatures, and
more non-ideal behavior at lower
temperatures. If the extent of non-ideal
behavior is large enough, unmixing or
immiscibility may be seen at lower
temperatures. If, for example, alkali feldspar
end members mixed ideally, there would be
no solvus in the alkali feldspar system.
µ of the almandine (Fe3Al2Si3O12) component
of a garnet solid solution ((Fe, Mg, Ca,
Mn)3Al2Si3O12) is
µalm = µ °alm + RT lnaalm
µ° is chemical potential of component in its
pure reference state the activity forms a
bridge between idealized behavior and real
behavior
 Solutions: T-X relationships
Example: orthopyroxenes (Fe, Mg)SiO3
– Real vs. Ideal Solution Models

Figure 27.3. Activity-composition relationships for the enstatite-ferrosilite mixture in orthopyroxene at 600 oC and 800oC. Circles are data
from Saxena and Ghose (1971); curves are model for sites as simple mixtures (from Saxena, 1973) Thermodynamics of Rock-Forming
Crystalline Solutions. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
 Activity Models (Activity-Composition
Relations) for Crystalline Solutions
• aprp = γMg3XMg3
• aalm = γ Fe3XFe3
• agrs = γ Ca3XCa3
• asps = γ Mn3XMn3
If we assume ideal behavior (γ = 1) in garnet
• aalm = Xalm3 = [Fe/(Fe + Mg + Ca + Mn)]3
• aprp = Xprp3 = [Mg/(Fe + Mg+ Ca + Mn)]3
......................................................
 The Equilibrium Constant

• At equilibrium the sum of the Gibbs free energies of

the reactants equals the sum of the Gibbs free
energies of the products.
• Equally, the sum of the chemical potentials of the
reactants equals chemical potentials of the products.
• aA + bB = cC + dD
At equilibrium for component i Δ rµ i= 0 = cµ i C + dµ i D
- aµ i A - bµ i B
• If we then remember that µ - µ ° = RT lna
• and rewrite it as µi = µi ° + RT lna
• we can reformat for component i the earlier equation
as Δ rµ = 0 = c(µ C° + RT lnaC) + d(µD° + RT lnaD) - a(µA° +
RT lnaA) - b(µB° + RT lnaB)
or, Δ rµ = Δ rµ ° + RT ln (aCc aDd/aAa aBb)
or. Δ rµ = Δ rµ ° + RT ln Q
and Q is the activity product ratio. The activities in
the Q term change as the reaction progresses toward
equilibrium, Δ rµ=0
• At equilibrium, the product and reactant activities
have adjusted themselves such that Δ rµ = 0.
We write this (with K instead of Q, to signify
equilibrium) as 0 = Δ rG° = -RT ln K

• The utility of K is that it tells us for any reaction

and any pressure and temperature, what the
activity ratios of the phases will be at equilibrium
 Solutions: T-X relationships
Back to our reaction:
Simplify for now by ignoring dP and dT
For a reaction such as:
aA + bB = cC + dD
At a constant P and T:
Δ G P , T = Δ G oP , T + R ln K
c
ac aD d T
where: K =
a b
aA aB
c d c d
Xc XD γc γD
K= =KD.Kγ
XA a XB b γ A a γ B b
 Compositional variations
Effect of adding Ca to jadeite + quartz=albite plagioclase
= Al-rich Cpx + Q
ΔGT, P = ΔGoT, P + RTlnK
Let’s say ΔGoT, P was the value that we calculated for
equilibrium in the pure Na-system (= 0 at some P and T)
ΔGoT, P = ΔG298, 0.1 + ΔV (P - 0.1) - ΔS (T-298) = 0
By adding Ca we will shift the equilibrium by RTlnK
We could assume ideal solution and
Pyx Q
X Jd XSiO 2
K= Plag
All coefficients = 1
X Ab
 Solutions: T-X relationships
Ab = Jd + Q was calculated for pure phases
When solid solution results in impure phases
the activity of each phase is reduced
 Compositional variations
Effect of adding Ca to jadeite + quartz = albite
ΔGP, T = ΔGoP, T + RTlnK
numbers are values for K

Figure 27.4. P-T phase diagram for the reaction Jadeite + Quartz = Albite for various values of K. The equilibrium curve for K = 1.0 is the
reaction for pure end-member minerals (Figure 27.1). Data from SUPCRT (Helgeson et al., 1978). Winter (2010) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.
 Geothermobarometry
Use measured distribution of elements in coexisting
phases from experiments at known P and T to estimate
P and T of equilibrium in natural samples
 Thermometry
Exchange Reactions
• Many thermometers are based on exchange
reactions, which are reactions that exchange
elements but preserve reactant and product
phases.
• For example: Fe3Al2Si3O12+ KMg3AlSi3O10(OH)2 =
Mg3Al2Si3O12 + KFe3AlSi3O10(OH)2
• almandine + phlogopite = pyrope + annite
We can reduce this reaction to a simple exchange
vector: (FeMg)gar+1 = (FeMg)bio-1
• Popular thermometers include garnet-biotite (GARB),
garnet-clinopyroxene, garnet-hornblende, and
clinopyroxene-orthopyroxene; all of these are based
on the exchange of Fe and Mg, and are excellent
thermometers because ΔrV is small, such that
dP/dT= ΔrS/ ΔrV is large (i.e., the reactions have steep
slopes and are little influenced by pressure).
Let's write the equilibrium constant for this exchange
reaction K = (aprpaann)/(aalmaphl)
• thus ΔrG = -RT ln (aprpaann)/(aalmaphl)
• If we assume ideal behaviour, The equilibrium constant is
K = KD=(XMggar XFebio)/(XFegar XMgbio)
• When discussing element partitioning it is common to
define a distribution coefficient KD, which is just the
equilibrium constant without the exponent (this just
describes the partitioning of elements and not the
partitioning of chemical potential):
KD = (XMggar XFebio)/(XFegar XMgbio) = (Mg/Fe)gar /(Mg/Fe)bio =
K1/3
• John Ferry and Frank Spear in 1978 measured experimentally the
distribution of Fe and Mg between biotite and garnet at 2 kbar and
found the following relationship:
 Geothermobarometry
The Garnet - Biotite geothermometer
 K=KD.Kγ, therefore, lnK= lnKD + lnKγ
• If you compare their empirical equation
If we compare this relation with
ln KD = -2109 / T + 0.782 ln K = - ( G° / RT) = -( H / RT) - (P V /
r r r
RT) + (rS / R)
As in case of ideal solution, ln K =ln
KD

for this reaction rS = 3*0.782*R =

19.51 J/mol K
(the three comes from the site
occupancy coefficient; i.e., K = KD3)
and -(rH / R) - (PrV / R) = -2109
= 3*2109*R -2070*rV

or rH
As value of m (tanangent of its inclination, m = tan θ) decreases angle decreases wrt to
x axis (which is T in a P-T diagram)

Therefore, if the reaction has lower value for rV, the slope [dP/dT=∆S/ ∆V(rV)] will be
high, so the angle with T will be increasing- very sensitive to temperature, good
thermometry

Therefore, if the reaction has larger value for rV, the slope will be small, so the angle
with T will be decreasing- insensitive to temperature good barometry
 Volume change

• Molar volume measurements show that for

this exchange reaction rV = 0.238 J/bar, thus
r
H = 52.11 kJ/mol
• The full equation is then 52,110 - 19.51*T(K) +
0.238*P(bar) + 3RT ln KD = 0
• To plot the KD lines in PT space
 Geothermobarometry
The Garnet - Biotite geothermometer

lnKD = -2108 · T(K) + 0.781

ΔGP,T = 0 = ΔH 0.1, 298 - TΔS0.1, 298 + PΔV + 3 RTlnKD

lnKD

Figure 27.5. Graph of lnK vs. 1/T (in Kelvins) for the Ferry and Spear (1978) garnet-biotite exchange equilibrium at 0.2 GPa from Table
27.2. Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
• To plot the KD lines in PT space
•
 Geothermobarometry
The Garnet - Biotite geothermometer

Figure 27.6. AFM projections showing the relative distribution of Fe and Mg in garnet vs. biotite at approximately 500 oC (a) and 800oC (b).
From Spear (1993) Metamorphic Phase Equilibria and Pressure-Temperature-Time Paths. Mineral. Soc. Amer. Monograph 1.
 Barometry
• Net-Transfer Reactions
Net-transfer reactions are those that cause phases to
appear or disappear. Geobarometers are often based on net-
transfer reactions because ΔrV is large and relatively insensitive to
temperature.
A popular one is GASP:
3CaAl2Si2O8 = Ca3Al2Si3O12 + 2Al2SiO5 + SiO2
anorthite = grossular + kyanite + quartz

which describes the high-pressure breakdown of anorthite.

For this reaction, rG = -RT ln [(aqtzaky2agrs) / aan3] = -RT ln agrs /
aan3
• (the activities of quartz and kyanite are one because they are pure
phases). A best fit through the experimental data for this reaction
by Andrea Koziol and Bob Newton yields P(bar) = 22.80 T(K) - 7317
• for Δ rV = -6.608 J/bar. Again, if we use ln K = -(Δ rH / RT) - (P Δ rV / RT)
+ (Δ rS / R)
• and set ln K = 0 as they calculated for pure composition
• So, we can rewrite the above as
(P Δ rV / R) = -(Δ rH / R) + (T Δ rS / R)
Or, P= TΔ rS /Δ rV - Δ rH / Δ rV (dividing both side by R/ Δ rV )

• if T Δ rS / Δ rV = 22.8, then Δ rS = -150.66 J/mol K

if Δ rH / Δ rV = 7317 then Δ rH = -48.357 kJ/mol

• So, we can write the whole equation as 0 = -48,357 + 150.66 T(K)

-6.608 P (bar) + RT ln K
• Contours of ln K on a PT diagram for GASP look like this:
• To plot the KD lines in PT space
•
 Sources of error in thermobarometry
1. The assumption that the minerals record equilibrium conditions may not be valid.
2. The choice of mineral compositions to use in thermobarometric calculations is
easy if all phases are homogeneous, but if minerals are zoned, the selection of
compositions to use can be more uncertain.
3. The stability of minerals may be affected by the presence of elements that are
difficult to analyze with standard techniques. For example, electron microprobe analyses do
not distinguish between Fe 2+ and Fe 3+, but the difference is important. A thermobarometric calculation
may be substantially in error if all Fe is assumed to be Fe 2+ for minerals that contain substantial Fe 3+.
4. Thermobarometric calculations rely on thermodynamic data and a 'calibration'
that allows mineral composition to be related to temperature or pressure. The
mineral compositions and crystal structures in the rock being analyzed should not
be too different from the compositions and structures on which the calibrations
are based.
5. Temperature calculations require an estimation of pressure, and pressure
calculations require an estimation of pressure. You therefore either need to know
one variable, or use a thermometer or barometer that is very insensitive to the
other variable. Hence, the best thermometers have nearly vertical slopes on a P-T
diagram and the best barometers have nearly horizontal slopes.
 Geothermobarometry
P-T-t Paths

Figure 27.14. Chemically zoned plagioclase and poikiloblastic garnet from meta-pelitic sample 3, Wopmay Orogen, Canada. a. Chemical
profiles across a garnet (rim → rim). b. An-content of plagioclase inclusions in garnet and corresponding zonation in neighboring plagioclase.
After St-Onge (1987) J. Petrol. 28, 1-22 .
 Geothermobarometry
P-T-t Paths

Figure 27.15. The results of applying the garnet-biotite geothermometer of Hodges and Spear (1982) and the GASP geobarometer of Koziol
(1988, in Spear 1993) to the core, interior, and rim composition data of St-Onge (1987). The three intersection points yield P-T estimates
which define a P-T-t path for the growing minerals showing near-isothermal decompression. After Spear (1993).
 What is a P-T-t path
Metamorphism is a
• Dsc xx dynamic process,
involving changes in
temperature ± pressure
through time. The
pressure (P) -
temperature (T) - time (t)
A common pressure-temperature path for regional metamorphism. The
rate of prograde metamorphism (heating) and rate of retrograde
path of a metamorphic
metamorphism (cooling) may not be the same. The duration of the path
from start (onset of metamorphism) to finish (exposure of the rock at the
rock is the set of all P-T
Earth's surface) will vary from rock to rock depending on the tectonic
history
conditions experienced
by a rock during its
metamorphic history
 What are some common P-T paths?

• P-T paths are commonly described as 'clockwise' or

'anticlockwise' (a.k.a. 'counterclockwise').

• Paths can be clockwise or anticlockwise, and can also

vary in terms of
` (1) how different the prograde and retrograde segments
of the path are – very similar or very different (Figure
2b), and
(2) how different the maximum pressure and maximum
temperature are from each other (Figure 2c).
Common P-T paths, including (a) Clockwise versus counterclockwise
paths, (b) Paths with similar vs different prograde and retrograde
segments, and (c) Paths with coincident maximum P and T conditions
vs paths with very different maximum P and T conditions. Note that
the T maximum is known as the 'peak' of metamorphism.
How are P-T paths determined?
 How are P-T paths determined?
• For some rocks, the only part of the P-T path recorded in the mineral assemblage
and texture of the rock is the 'peak' of metamorphism – the conditions of the
thermal maximum (i.e., the maximum temperature and the pressure at the
maximum temperature).

• At the peak of metamorphism, the mineral assemblage presumably equilibrated,

and no (or little) further reaction took place as the rock cooled and decompressed
en route to the Earth's surface.

• Some rocks may record more of their P-T paths. If a rock contains a partial record of
its P-T path, this is both good and bad. This is good because we want as much P-T
path information as possible, so as to be able to interpret the thermal/tectonic
processes and history as well as possible. This is bad because the mineralogical and
textural evidence for P-T path segments other than the conditions of the peak of
metamorphism represent disequilibrium. In most cases, however, the evidence for
disequilibrium can be very useful because it can be used to reconstruct P-T path
segments.
• A few common methods for inferring P-T path
segments are:
1. Mineral inclusions
Some minerals contain inclusions of other minerals.
For example, garnets commonly contain inclusions of
minerals that were present in the rock matrix as the
garnet grew, but that were not completely eliminated
by metamorphic reactions during progressive
metamorphism. The growing garnets surrounded
these relict minerals as the garnets grew, and the
relict minerals are preserved as mineralogical evidence
of an earlier stage in the metamorphic history of the
rock.
Figure 3. Left: Photomicrograph (plane light) of kyanite inclusions in garnet; field of view = 2 mm. Right: Photomicrograph (crossed polars) of
sillimanite in the matrix; field of view = 4 mm.

Figure 3. Left: Photomicrograph (plane light) of kyanite inclusions in garnet; field

of view = 2 mm. Right: Photomicrograph (crossed polars) of sillimanite in the
matrix; field of view = 4 mm.
•Some inclusions don't contain a lot of information
about P-T conditions because the minerals are stable
over such a wide range of conditions (for example:
quartz).
•Other mineral inclusions are very useful for inferring
P-T conditions and path segments, especially if these
minerals no longer exist in the matrix of the rock (that
is, outside the garnet).
•In Figure 3, kyanite inclusions occur in garnet in a rock
that has only sillimanite in the matrix, indicating that
the rock was previously in the kyanite stability field but
that P-T conditions changed. When the matrix of the
rock (including the garnet rim) equilibrated, the rock
was in the silliminate stability field (Fig. 4).
• Figure 4. P-T diagram showing
stability fields of the Al2SiO5
polymorphs: andalusite,
kyanite, and sillimanite (after
Holdaway, 1971). Two
possible P-T paths are shown
to illustrate different ways
that kyanite can be replaced
by sillimanite: one path (a)
involves a decrease in
pressure (decompression);
the other (b) involves an
increase in temperature
(prograde metamorphism).
Even though it may not be possible to determine the
trajectory of the P-T path from inclusions alone,
inclusions may be used with other chemical and
textural information to better define the path. In
addition, the composition of inclusions may be used in
thermobarometry to determine P-T conditions along
the path, provided the inclusions have not chemically
reacted with their host mineral (e.g., Whitney, 1991).
2. Element zoning
• Metamorphic (and igneous) minerals may change composition in response
to changing chemical and physical conditions, such as changes in
pressure-temperature conditions, deformation variables, or chemical
factors (e.g., presence of fluids). The chemical response of a mineral to
these changes may be recorded in minerals that have crystal chemical and
structural characteristics that allow compositions acquired early in the
mineral's growth history to be preserved during later stages of growth at
different conditions. Crystals that have different regions with different
compositions are zoned .
• A very common zoning pattern involves a difference in composition of a
mineral's center (core) compared to its rim, and concentric rings of
different compositions arranged between the core and the rim (Fig. 5).
Minerals that typically show this type of zoning in the major or trace
elements are garnet, plagioclase, zircon, and tourmaline (Fig. 5). Of these,
garnet and plagioclase are relevant to studies of metamorphic P-T paths,
and zircon is relevant to determination of the timing of petrologic events.
 Geothermobarometry
P-T-t Paths

Figure 27.14. Chemically zoned plagioclase and poikiloblastic garnet from meta-pelitic sample 3, Wopmay Orogen, Canada. a. Chemical
profiles across a garnet (rim → rim). b. An-content of plagioclase inclusions in garnet and corresponding zonation in neighboring plagioclase.
After St-Onge (1987) J. Petrol. 28, 1-22 .
Figure 5. Common zoned minerals. (a) False color X-ray map showing Mn distribution
in a garnet from Iran (Sepahi et al., 2003). The garnet core contains more Mn than
the garnet rim (or the matrix); this is typical growth zoning. The garnet is 1.3 mm in
diameter; (b) Photomicrograph (crossed polarized light) showing zoning in
plagioclase in a metamorphosed igneous rock; oscillatory zoning is common in
igneous plagioclase, but metamorphic plagioclase may also be zoned in the anorthite
(Ca) and albite (Na) components; field of view = 2 mm; (c) Photomicrograph (plane
polarized light) of a zoned tourmaline crystal in a kyanite schist; field of view = 2 mm;
(d) Cathodoluminescence image of isotopically zoned zircon from the Nigde Massif,
Turkey, with the U-Pb age of the core and rim labeled in millions of years (Whitney
et al., 2003).
• Using zoning information to reconstruct the part of the P-T path
experienced by the zoned mineral is not simple, but a few general aspects
of the relationship of zoning to P-T path may easily be inferred:
(a) Garnets with Mn-rich cores and Mn-poorer rims record growth zoning
that represents the change from the lower-T conditions at which the
garnet core grew to the higher-T conditions at which the garnet rim grew
(i.e., prograde metamorphism involving increasing temperature and
pressure). Mn is preferentially partitioned into garnet relative to most
other common minerals, so Mn is sequestered in early-formed garnet,
depleting the local environment of the growing garnet in Mn.
(b) Minerals that show major element growth zoning probably did not
experience very high metamorphic temperatures. At high temperature (>
700 C) and sufficient duration, zoning may be homogenized as
intracrystalline diffusion becomes more effective at eliminating
compositional variation. An unzoned mineral that is typically zoned at
low-medium metamorphic grades has either experienced high
temperature conditions or was never zoned (owing to a simple reaction
history at limited P-T or to growth entirely at high-T).
3. Reaction textures
• Some metamorphic rocks contain evidence for incomplete
reactions or other textural evidence for part of the P-T path. A
simple example is the partial replacement of andalusite by
sillimanite (Fig. 6a) by the polymorphic transformation of
andalusite to sillimanite. Textural evidence may also be useful in
cases where the reactants have been completely consumed if the
shape of one or more reactants are preserved; for example,
pseudomorphs(Figs. 6b-d).
An example of a more complex reaction texture involves the
formation of coronas , which consist of one or more shells (rims,
moats) of a mineral or minerals around a central (reactant) phase
(Fig. 6e). In many cases, coronas also involve the fine-scale
intergrowth of minerals in a texture known as symplectite(Figs.
6e-f).
Figure 6. Images of reaction textures. (a) Photomicrograph (plane light) showing the partial replacement of andalusite by
sillimanite in a schist from Iran. Note: The crystallization sequence (sillimanite after andalusite) can't be inferred only from this
photo; (b) Photomicrograph (plane light) showing the complete replacement of kyanite by sillimanite in a sample of gneiss from
the Thor-Odin dome, British Columbia. The former presence of kyanite is known because some pseudomorphs (not shown)
contain relict kyanite. Without these relics, and based only on the tabular shape of the pseudomorph, it would be difficult to
infer whether the original mineral was kyanite or andalusite; (c) Crossed polar view of (b) showing the randomly oriented
sillimanite in the pseudomorph; (d) Photomicrograph (plane light) showing a partial pseudomorph of chlorite after garnet from a
retrograded eclogite, Turkey. Garnet relics are present, but the former presence of garnet is clear also from the shape of the
pseudomorph; (e) Photomicrograph (plane light) showing a corona texture from a Thor-Odin dome gneiss. The central Al2SiO5
phase (sillimanite after kyanite) is rimmed by an inner shell of spinel + cordierite symplectite and an outer shell of cordierit; (f)
Backscattered electron image of spinel (brightest phase) + cordierite (darkest gray) + anorthite (medium gray) from a Thor-Odin
symplectite.
 How are P-T-t paths interpreted?

• An important part of using P-T paths or P-T-t paths to understand

metamorphic and tectonic processes is to relate the P-T
conditions, path shape, and (if age information is available)
duration and rate of P-T path segments to the driving forces of
metamorphism.
• P-T path shape by itself does not provide a unique interpretation
of tectonic process or metamorphic driving forces. For example,
clockwise paths can form in continental collision belts of
subduction zones. Similarly, some subduction zone rocks record
clockwise paths and some record counterclockwise paths.
However, the integration of P-T path characteristics, time/rate
information, structural data, and other petrologic information
can provide significant information about metamorphic and
tectonic processes. Therefore, although subduction zone rocks
can follow various paths during subduction and exhumation,
determining the specific path that a particular exhumed
subduction zone rock followed is important for understanding
subduction dynamics.
 Integrating deformation into P-T-t
histories: P-T-t-d paths
• The idealized view of P-T paths is that mineral assemblages equilibrate
at every stage of the path from the onset of metamorphism to the peak
of metamorphism, at which the final assemblage is locked in.
• It is important to recognize the influence of deformation on metamorphic
reactions, and the extent to which deformation (strain energy) may assist
reactions. It is possible that two rocks of the same bulk composition that
follow the same P-T path but that have different deformation histories
(e.g., one is pervasively deformed and the other is not, perhaps because
strain is localized in weaker rocks nearby) will contain different mineral
assemblages. The deformed rock may contain the predicted equilibrium
assemblage for the P-T conditions attained by the rock, whereas the
undeformed or less deformed rock may contain more metastable
phases. P-T conditions and paths should therefore be considered in their
structural context, and, if possible, a P-T-t-d path
(Pressure-Temperature-time-deformation) constructed.
Slides not used
•
Gibbs–Duhem’s equation
For a system at equilibrium, the Gibbs-Duhem equation must hold:∑nidμi=0….(1)
at a constant pressure and temperature dG = Σ μidni
• This relationship places a compositional constraint upon any changes in the chemical
potential in a mixture at constant temperature and pressure for a given composition. This
result is easily derived when one considers that μi represents the partial molar Gibbs
function for component i . And as with other partial molar quantities,
• Gtot=∑niμi…(2)
• Taking the derivative of both sides yields
dGtot=∑inidμi+∑iμidni…..(3)
• But dG can also be expressed as
dG=Vdp−sdT+∑μidni……(4)
• Setting these two expressions equal to one another
∑nidμi+∑μidni=Vdp−sdT+∑μidni…..(5)
• And after canceling terms, one gets
∑nidμi=Vdp−sdT………(6)
• For a system at constant temperature and pressure
Vdp−sdT=0……(7)
• Substituting Equation 7 into 6 results in the Gibbs-Duhem equation (Equation 1 ). This
expression relates how the chemical potential can change for a given composition while
the system maintains equilibrium. So for a binary system, consisting of components A and
B (the two most often studied compounds in all of chemistry)
nBdμB=−nA/dμA……..(8)
Ignoring (for a while) heat capacity, thermal expansion and isothermal
compression…
• If a chemically closed system has two possible states (configurations of
phases), the one with the lowest absolute G at any PT should be more
stable.
• If both have the same absolute G (the ∆G of moving from one state to
the other = 0), they have the same relative stability and a reaction
between them is stable.
 Fugacity
• https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemi
stry_Textbook_Maps/DeVoe's_%22Thermodynamics_and_Chemistry%22/
07%3A_Pure_Substances_in_Single_Phases/7.8_Chemical_Potential_and_
Fugacity
• An ideal gas is in its standard state at a given temperature when its
pressure is the standard pressure. We find the relation of the chemical
potential of an ideal gas to its pressure and its standard chemical potential
at the same temperature by setting Vm equal to RT/p in Eq. 7.8.5: μ(pʹ)
−μ∘=∫pʹp∘(RT/p)dp=RTln(pʹ/p ∘). The general relation for μ as a function of
p, then, is
μ=μ∘(g)+RTln(p/p∘)(pure ideal gas, constant T)
• If a gas is not an ideal gas, its standard state is a hypothetical state. The
fugacity, f , of a real gas (a gas that is not necessarily an ideal gas) is
defined by an equation with the same form as Eq. 7.8.6:
μ=μ∘(g)+RTln(f/p∘) (pure gas)
• Note that fugacity has the dimensions of pressure. Fugacity is a kind of
effective pressure. Specifically, it is the pressure that the hypothetical
ideal gas (the gas with intermolecular forces “turned off” ) would need to
have in order for its chemical potential at the given temperature to be the
same as the chemical potential of the real gas (see point C in Fig. 7.6). If
the gas is an ideal gas, its fugacity is equal to its pressure.
• In the Fig. Chemical potential as a function of pressure at constant temperature,
for a real gas (solid curve) and the same gas behaving ideally (dashed curve).
Point A is the gas standard state. Point B is a state of the real gas at
pressure p′p′. The fugacity f(p′)f(p′) of the real gas at pressure p′p′ is equal to
the pressure of the ideal gas having the same chemical potential as the real gas
(point C).
 Entropy as a Measure of Disorder

• Perhaps the best way to understand entropy as a driving force in nature is to conduct a simple
experiment with a new deck of cards. Open the deck, remove the jokers, and then turn the deck
so that you can read the cards. The top card will be the ace of spades, followed by the two, three,
and four of spades, and so on. Now divide the cards in half, shuffle the deck, and note that the
deck becomes more disordered. The more often the deck is shuffled, the more disordered it
becomes.What makes a deck of cards become more disordered when shuffled?
• In 1877 Ludwig Boltzmann provided a basis for answering this question when he introduced the
concept of the entropy of a system as a measure of the amount of disorder in the system. A
deck of cards fresh from the manufacturer is perfectly ordered and the entropy of this system is
zero. When the deck is shuffled, the entropy of the system increases as the deck becomes more
disordered.
• There are 8.066 x 1067 different ways of organizing a
deck of cards. The probability of obtaining any
particular sequence of cards when the deck is
shuffled is therefore 1 part in 8.066 x 1067. In theory, it is
possible to shuffle a deck of cards until the cards fall into perfect order. But it isn't very likely!
• Boltzmann proposed the following equation to describe the relationship between entropy and the
amount of disorder in a system.

• S = k ln W

• In this equation, S is the entropy of the system, k is a proportionality constant equal to the ideal
gas constant divided by Avogadro's constant, ln represents a logarithm to the base e, and W is the
number of equivalent ways of describing the state of the system. According to this equation, the
entropy of a system increases as the number of equivalent ways of describing the state of the
system increases.

• The relationship between the number of equivalent ways of describing a system and the amount
of disorder in the system can be demonstrated with another analogy based on a deck of cards.
There are 2,598,960 different hands that could be dealt in a game of five-card poker. More than
half of these hands are essentially worthless. Winning hands are much rarer. Only 3,744
combinations correspond to a "full house," for example. The table below gives the number of
equivalent combinations of cards for each category of poker hand, which is the value of W for this
category. As the hand becomes more disordered, the value of W increases, and the hand becomes
intrinsically less valuable.
Number of Equivalent Combinations for Various Types of Poker Hands

Hand W ln W
Royal flush
(AKQJ10 in one 4 1.39
suit)
Straight flush (five
cards in sequence 36 3.58
in one suit)
Four of a kind 624 6.44
Full house (three
of a kind plus a 3,744 8.23
pair)
Flush (five cards in
5,108 8.54
the same suit)
Straight (five cards
10,200 9.23
in sequence)
Three of a kind 54,912 10.91
Two pairs 123,552 11.72
One pair 1,098,240 13.91
No pairs 1,302,540 14.08
The Relationship Between Free Energy
and Cell Potential
• The value of ΔG for a reaction at any moment in time
tells us two things. The sign of ΔG tells us in what
direction the reaction has to shift to reach equilibrium.
The magnitude of ΔG tells us how far the reaction is
from equilibrium at that moment.

• The potential of an electrochemical cell is a measure

of how far an oxidation-reduction reaction is from
equilibrium. The Nernst equation describes the
relationship between the cell potential at any moment
in time and the standard-state cell potential.
• Let's rearrange this equation as follows.
nFE = nFEo - RT ln Q

• We can now compare it with the equation used to describe the relationship between
the free energy of reaction at any moment in time and the standard-state free
energy of reaction.

ΔG = ΔGo + RT ln Q

• These equations are similar because the Nernst equation is a special case of the
more general free energy relationship. We can convert one of these equations to the
other by taking advantage of the following relationships between the free energy of
a reaction and the cell potential of the reaction when it is run as an electrochemical
cell.

ΔG = -nFE
• Therefore, we introduce the concept of
enthalpy (H), which is the sum of the internal
energy of the system plus the product of the
pressure of the gas in the system times the
volume of the system.
H = E + PV

Δ H = Δ E + Δ (P V)
The Relationship Between Free Energy
and Cell Potential
• The value of ΔG for a reaction at any moment in time
tells us two things. The sign of ΔG tells us in what
direction the reaction has to shift to reach equilibrium.
The magnitude of ΔG tells us how far the reaction is
from equilibrium at that moment.

• The potential of an electrochemical cell is a measure

of how far an oxidation-reduction reaction is from
equilibrium. The Nernst equation describes the
relationship between the cell potential at any moment
in time and the standard-state cell potential.
• Let's rearrange this equation as follows.
nFE = nFEo - RT ln Q

• We can now compare it with the equation used to describe the relationship between
the free energy of reaction at any moment in time and the standard-state free
energy of reaction.

ΔG = ΔGo + RT ln Q

• These equations are similar because the Nernst equation is a special case of the
more general free energy relationship. We can convert one of these equations to the
other by taking advantage of the following relationships between the free energy of
a reaction and the cell potential of the reaction when it is run as an electrochemical
cell.

ΔG = -nFE
• A good example of this phenomenon is the reaction in which NO2
dimerizes to form N2O4.

• 2 NO2(g) <---> N2O4(g)

• This reaction is favored by enthalpy because it forms a new bond,

which makes the system more stable. The reaction is not favored
by entropy because it leads to a decrease in the disorder of the
system.

• NO2 is a brown gas and N2O4 is colorless. We can therefore

monitor the extent to which NO2 dimerizes to form N2O4 by
examining the intensity of the brown color in a sealed tube of this
gas. What should happen to the equilibrium between NO2 and
N2O4 as the temperature is lowered?
 The Laws of Thermodynamics

First law: Energy is conserved; it can be neither created nor

destroyed.

Second law: In an isolated system, natural processes are

spontaneous when they lead to an increase in disorder, or entropy.

Third law: The entropy of a perfect crystal is zero when the

temperature of the crystal is equal to absolute zero (0 K).

There have been many attempts to build a device that violates the
laws of thermodynamics. All have failed. Thermodynamics is one of the
few areas of science in which there are no exceptions.
• For the sake of argument, let's assume that there is no significant
change in either ΔHo or ΔSo as the system is cooled. The
contribution to the free energy of the reaction from the enthalpy
term is therefore constant, but the contribution from the entropy
term becomes smaller as the temperature is lowered.

• ΔGo = ΔHo - T ΔSo

• As the tube is cooled, and the entropy term becomes less

important, the net effect is a shift in the equilibrium toward the
right. The figure below shows what happens to the intensity of the
brown color when a sealed tube containing NO2 gas is immersed
in liquid nitrogen. There is a drastic decrease in the amount of
NO2 in the tube as it is cooled to -196oC.
 NOT USED
• Exothermic vs. Endothermic
• If Δ rH° < 0 the reaction produces a reduction in
enthalpy and is exothermic (heat is given up by the
rock and gained by the surroundings). If Δ rH° > 0 the
reaction produces an increase in enthalpy and is
endothermic (heat from the surroundings is consumed
by the rock). An easy way to remember this is that
spontaneous reactions produce a decrease in internal
energy, and because we know that
E P ∞ HP
a decrease in HP is also a decrease in EP.
Source:https://www.sydney.edu.au/science/chemistry/~george/1405/Wk4-6.pdf