Lecture 6

Basic equations
(applicable only for closed system)
Gibbs-Helmholtz Equation
Free energy
Case I: Consider a system contained in
a vessel equipped with a freely movable
piston and diathermal walls, allowing
mechanical and thermal equilibrium to
be established with its surroundings -
i.e. p and T are uniform.
System and surroundings can exchange
heat and pV work only, subject to the
constraints
The Second Law implies that during a spontaneous
isobaric/isothermal change in a closed system the Gibbs energy
always decreases. This continues until G reaches a
minimum as the system settles in its equilibrium state.

In Fig. could be any parameter characterising the state of the

system, for example a measure for the progress of a chemical
reaction,
 Case II: Consider a system containing in a rigid vessel (constant
V, e.g. a bomb calorimeter) and is only in thermal contact with the
surroundings, so T is uniform.

The functions like G and A try to attain minimum and hence referred as
thermodynamic potentials. The condition of minimum free energy bears
out the fact that a thermodynamic equilibrium is always the result of a
compromise between two opposing tendencies.
Firstly, the system tends to settle in a state of lowest (potential) energy,
while on the other hand the randomising effect of the thermal motion of
the molecules at finite T leads to occupation of higher energy states and
increased entropy. This is the reason why S appears with a weight
factor T.
Variation of G with T and p

dG vdp SdT
G G
S ; V
T p p T
 G
S
T p
 G
V
p T
 Expansion of a gas

dG Vdp
dp p
G nRT nRT ln 2
p p1
p2
G G nRT ln
0

p1
p2
G G nRT ln 0
0

p
G G0 p
RT ln 20
n n p
G G0 p2
RT ln 0
n n p
Chemical potential p
0 RT ln 20
p
The chemical potential of a pure substance

G

n T , p

For a pure substance,

G=n.Gm

p
RT ln 0
0

p
The chemical potential of real gases

As p0, matches with ideal

gas behavior. At intermediate
pressures, where attractive
forces dominant is less than
for an ideal gas molecules
have lower escaping tendency.
At high pressures where
repulsive forces dominate, real
is greater than ideal gas.

f
RT ln 0
0

p
The standard state of a real gas is a hypothetical state in which the gas is at a
pressure p0 and behaving ideally.
Phase equilibrium of a pure
substance

e.g.: n moles of water

Energy balance
Note: When we consider the equilibrium between water vapor and water
liquid (in a closed system), the pressure relates to the vapor pressure
above liquid water. Do not get confused with atmospheric pressure. For
general calculations, you can assume H is constant. Otherwise, use Cp
values of liquid and vapor to calculate H at different temperatures.
 Phase diagram

You are expected to learn

construction and use of a typical phase diagram

Use of phase diagrams to identify stable phases at

given T & p and to describe phase transitions

Significance and the use of supercritical fluid phase of

matter
Phase diagram is a graphical representation of all the
equilibrium phases as a function of temperature, pressure, and
composition.

Component - chemically recognizable species (H2O, C, NaCl in

water). A salt solution contains two components, acid or base
solution contains two components, concentrated acids one
component?).

For one component systems, the equilibrium state of the

system is defined by two independent parameters (P and
T), (T and V), or (P and V).

Phase a portion of a system that has uniform physical and

chemical characteristics. Two distinct phases in a system have
distinct physical and/or chemical characteristics (e.g. water and ice,
water and oil) and are separated from each other by definite phase
boundaries. A phase may contain one or more components. A
single-phase system is called homogeneous, systems with two or
more phases are mixtures or heterogeneous systems.
A system is at equilibrium if at constant temperature, pressure and
composition the system is stable, not changing with time.

Equilibrium is the state that is achieved given sufficient time. But the time to
achieve equilibrium may be very long (the kinetics can be slow) that a state
along the path to the equilibrium may appear to be stable. This is called a
metastable state.
In thermodynamics the equilibrium is described
as a state of a system that corresponds to the
minimum of thermodynamic function called the
free energy. Thermodynamics tells us that:
Equilibrium and Metastable States
Under conditions of a constant temperature
and pressure and composition, the direction of
any spontaneous change is toward a lower
free energy.
The state of stable thermodynamic
equilibrium is the one with minimum free
energy.
A system at a metastable state is trapped in a
local minimum of free energy that is not the
global one.
 Phase diagram of water

Ice/water (freezing point

curve) is very special. It
has a negative slope
due to the fact that
when ice melts, the
molar volume
decreases. Ice actually
melts at lower
temperature at higher
pressure.

Chemical potential or molar Gibbs function are equal at the equilirbrium line
Q. Pressure cookers allow food to cook faster because the higher pressure inside
the pressure cooker increases the boiling temperature of water. A particular pressure
cooker has a safety valve that is set to vent steam if the pressure exceeds 3.4 atm.
What is the approximate maximum temperature that can be reached inside this
pressure cooker? Explain your reasoning.
 Sublimation curve refers T & p at
which ice and water vapor are in
equilibrium. Consider a point where ice
has a vapor pressure of ~0.20 kPa at
10 C. If we place a frozen sample in
vacuum with a pressure < 0.20 kPa,
ice will sublime. Freeze-drying
process often used to preserve foods,
such as the ice cream is based on this
principe..

Melting point curve refers ice and liquid water

equilibrium at different T & p. A slight negative slope
(most diagrams generally exaggerate the same)
indicates that the melting point for water decreases
slightly as pressure increases. Water is an unusual
substance as most substances exhibit an increase in
melting point with increasing pressure. This behavior
is partly responsible for the movement of glaciers.
The bottom of a glacier experiences an immense
pressure due to its weight that can melt some of the
ice, forming a layer of liquid water on which the
glacier may more easily slide.
Supercritical Fluids
A sample of water placed in a sealed vacuum
container (closed system) at 25 C and allowed to
establish vapour-liquid equilibrium would result in a
mixture of liquid water and water vapor at a
pressure of 0.03 atm (can you calculate??). A
distinct boundary between the more dense liquid
and the less dense gas would be seen. If we
increase the temperature, the pressure of the water
vapor increases (like in a pressure cooker), and the
two-phase equilibrium of liquid and water will
proceed. At 374 C, the vapor pressure has risen to
218 atm, and any further increase in temperature
results in the disappearance of the boundary
between liquid and vapor. All of the water in the
container is now present in a single phase whose
physical properties are intermediate between those
of the gaseous and liquid states. This phase of
matter is called a supercritical fluid, and the
temperature and pressure above which this phase
exists is the critical point. Above its critical
temperature, a gas cannot be liquefied no matter
how much pressure is applied. The pressure
required to liquefy a gas at its critical temperature is
called the critical pressure.
Many textbooks described ice skating as being possible
because the pressure generated by the skaters blade is
high enough to melt the ice under the blade, thereby
creating a lubricating layer of liquid water that enables
the blade to slide across the ice. Although this
explanation is intuitively satisfying, it is incorrect, as we
can show by a simple calculation.
A skater weighing 75kg (736 N) gliding on one foot, generates
a pressure ~ 15 atm on the ice. This is much lower than the
pressure needed to decrease the melting point of ice by even
1C (calculate dp/dT). Experience indicates that it is possible
to skate even when the temperature is well below freezing.
Thus pressure-induced melting of the ice cannot explain the
low friction that enables skaters (and hockey pucks) to glide.
Recent research indicates that the surface of ice, where the
ordered array of water molecules meets the air, consists of
one or more layers of almost liquid water. These layers,
together with melting induced by friction as a skater pushes
forward, appear to account for both the ease with which a
skater glides and the fact that skating becomes more difficult
below ~ 7C, when the number of lubricating surface water
layers decreases.
http://ergodic.ugr.es/termo/lecciones/water1.html
Since extreme pressures required to stabilize diamond, it is difficult to determine experimentally S and H
associated with the reaction C(graphite) C(diamond). We can extract these data from consideration of the
following reactions: graphite + O2 CO2 & diamond + O2 CO2.

(a) Calculate the changes in enthalpy and entropy associated with these two reactions at 298 K and 1 bar.
Combine these reactions to obtain H and S for the reaction: graphite diamond. Use these data to calculate
G for the reaction at 298K, 1 bar and indicate which polymorph is stable under these conditions.

(b) Write the general equation that describes the free energy change of a reaction at any temperature T and at the
reference Pr of 1 bar (i.e., at T = any T and P = Pr). Use this equation and the results from (a) to calculate the
free energy change of the graphite diamond reaction at 1300K and 1 bar.
Phase diagram of CO2: Its triple point is
well above 1 atm. It is impossible to get any
liquid CO2 at pressures less than 5.11
atmospheres. At normal condition CO2 will
sublime at a temperature of -78C.

The freezing point curve of CO2 has

a positive slope expected for any
substance.

Watch this video on youtube:

https://www.youtube.com/watch?v=G
Er3NxsPTOA
Q: If we shake a carbon dioxide fire extinguisher on a cool day (18 C), we can hear
liquid CO2 moving around inside the cylinder. However, the same cylinder appears to
contain no liquid on a hot summer day (35 C). Explain these observations.

Q. Dry ice, CO2(s), does not melt at atmospheric pressure. It sublimes at a temperature
of 78 C. What is the lowest pressure at which CO2(s) will melt to give CO2(l)? At
approximately what temperature will this occur?

Q. Ammonia can be liquefied by compression at room temperature; oxygen cannot be

liquefied under these conditions. Why do the two gases exhibit different behavior?
Supercritical fluids (H2O and CO2) have many commercial applications of late. For
example, CO2 has a low TC (31C) and comparatively low Tp (73 atm), and low
toxicity, making it easy to contain and relatively safe to manipulate. Because
many substances are quite soluble in supercritical CO2, commercial processes
that use it as a solvent are now well established in the oil industry, the food
industry, and others. Supercritical CO2 is pumped into oil wells that are no longer
producing much oil to dissolve the residual oil in the underground reservoirs. The
less-viscous solution is then pumped to the surface, where the oil can be
recovered by evaporation (and recycling) of the CO2.

In the food industry, being used to decaffeinate coffee, remove fats from potato
chips, and extract flavor and fragrance compounds from citrus oils. It is nontoxic,
relatively inexpensive, and not considered to be a pollutant. After use, the CO2 can
be easily recovered by reducing the pressure and collecting the resulting gas.
 NaCl-H2O system
eutectic point (-21C )
where ice and NaCl2H2O
are in equilibrium with the
saturated solution. Below
0.1C, NaCl.2H2O is the
stable form while above
NaCl is the stable form of
sodium chloride at
temperatures below
0.1C. The use of
sodium chloride as road
salt to dissolve ice in the
winter can be efficient at
temperatures down to the
eutectic point of the
solution. Below -21C
sodium chloride has no
effect on ice.

Question: Suppose you had a solution containing 15.0% by mass of NaCl,

and you cooled it from 15C to -30C. Describe and explain how what you
would see.
https://www.acs.org/content/dam/acsorg/education/resources/highschool/che
mmatters/articlesbytopic/solutions/chemmatters-feb2006-salting-roads.pdf

Cooling curve of 15% NaCl solution

PQ: natural cooling of the solution

At Q : separation of ice begins and
continue along QR
At R : Separation of eutectic mixture
(ice + NaCl.2H2O) begins and continue
along RS. Note the temperature halt is
Similar to a pure substance.
ST : Natural cooling of the mixture ice
and NaCl.2H2O
Try to answer the following questions:
(i) How many Kg of ice can 1 kg of NaCl melt at 250K?

(ii) The Dead Sea has a salinity of 33.7%. Assuming that this is the wt% of NaCl in
water, how many phases are present in the Dead Sea and what are they? If the
Indian Ocean is only 3.7 wt% NaCl on average, how many phases are present and
what are they? Assume a temperature of 250K.

(iii) The Titanic sank after hitting an iceberg. If the temperature was -2oC that night,
what was the salinity in the ocean in order to have the coexistence of ice and salt
water?

Watch the video: https://www.youtube.com/watch?v=Nw0aY3SXIdg

(iv) Brine, ice, and solid salt coexist at the eutectic temperature (21 C) and the
brine composition is the eutectic composition, 23.3% NaCl. The solid NaCl.2H2O
(not NaCl) and the ice are pure. Calculate its molality. If the cryoscopic constant
for water is 1.86 K kg mol1, predict a freezing point depression. Comment.
Dehydration of dil. aqueous CuSO4 solution T, p and composition diagram
at 500C. p versus composition diagram

Stability of copper sulphate hydrates: Salts are known to occur with

different degree of water of crystallization. CuSO4 occurs in four forms under
normal condition CuSO4.5H2O, CuSO4.3H2O, CuSO4.H2O and CuSO4
depending on the water vapor pressure (humidity). CuSO4.7H2O is known only
as mineral Boothite (see the structures in the next slides).

A mixture of salt (say CuSO4.5H2O and CuSO4.3H2O) in a closed system (e.g. a dessicator) controls
humidity/water vapor pressure. You can dry moist copper sulphate pentahydrate over the above mixture
in a desiccator.
 Stability of the salt
depends on water
vapour pressure

All salts occur

as minerals

CuSO4

CuSO4.H2O

CuSO4.5H2O

Note the
change in color
with varying
water of
crystallization 37
CuSO4.3H2O
 Nature reveals the secret!

Stalactites of melanterite [Fe(OH2)6.SO4.H2O]

along with Boothite hanging from a water pipe
(Richmond)
Boothite [{Cu(OH2)6}.SO4.H2O]: The crystal is made of the three
discrete molecules thru only hydrogen bonding interactions
no coordination bond between Cu2+ and sulphate unlike in the
previous four salt or salt hydrates!! This is an example of a
metastable phase. All the others are equilibrium or stable
phases under a specified condition. 38
The Canadian Mineralogist Vol. 41, pp. 937-949 (2003)
A tank contains 20 L of compressed nitrogen at 10 atm and 25C. Calculate the
work when the gas is allowed to expand reversibly and adiabatically to 1 atm
pressure. Assume that the gas behaves ideally.

Estimate the final temperature of one mole of gas at 200.0 atm and 19.0C as it
is forced through a porous plug to a final pressure of 0.95 atm. The Joule-
Thomson coefficient of the gas is 0.150 K/atm.
For temperatures below room temperature cooling
baths are used. A few examples are given below.
These baths consist of a solvent + something that
has a low temperature already (ice, ice/salt, dry ice,
or liquid nitrogen).