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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.
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
p
RT ln 0
0
p
The chemical potential of real gases
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
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
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
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..
(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.
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?
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.
(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?
(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
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
CuSO4
CuSO4.H2O
CuSO4.5H2O
Note the
change in color
with varying
water of
crystallization 37
CuSO4.3H2O
Nature reveals the secret!
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).