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Thermodynamics
Why thermodynamics are important in
pharmacy?
Energy
Voltage source
Mechanical Energy
A body is said to possess kinetic energy because of its motion or
the motion of its parts (i.e., its molecules, atoms, and electrons),
and to possess potential energy by virtue of its position or the
configuration of its parts.
It is not possible to know the absolute value of the energy of a
system; it is sufficient to record the changes in energy that occur
when a system undergoes some transformation.
Reversible processes
A process which is always in a state of virtual thermodynamic
equilibrium, being reversed by an infinitesimal change of
pressure, it is said to be reversible.
Maximum work
The work done by a system in an isothermal process
is at a maximum when it is done reversibly.
What is the maximum work done in
the isothermal reversible expansion of
1 mole of an ideal gas from 1 to 1.5
liters at 25C?
Wmax = - n RT ln (V2/V1)
Thermochemistry
Many chemical and physical processes are carried out at atmospheric (essentially
constant) pressure. Under this condition the work of expansion is done at constant
pressure, the heat exchanged equals to the change in enthalpy.
W = - P V = - P (V2 - V1)
E = Q + W
E = Qp - P (V2 - V1)
Qp is the heat absorbed at a constant pressure
Qp = E2 - E1 + P (V2 - V1)
Qp = E2 + PV2 - E1 + PV1 Qp = H (negative = exothermic, positive = endothermic)
enthalpy H
The increase in enthalpy H is equal to the heat absorbed at constant pressure
The change in enthalpy accompanying a chemical reaction remains a function only
of temperature.
Thermochemistry
The formation of methane:
C(s) + 2H2(g) == CH4(g)
Hf(25C)
The combustion of methane:
CH4(g) + 2O2(g) == CO2(g) + 2H2O(l)
Exercise: Thermochemistry
If breaking C=C bond requiring 130 kcal, breaking Cl-Cl bond requiring 57 kcal,
formation of C-C bond liberating 80 kcal and formation of C-Cl liberating 78
kcal of energy. What is the enthalpy change H of the reaction of ethene and
chlorine into dichlorethane?
1 cal = 4.184 joules
Exercise
H and S for the transition from liquid water to ice at -10C and at 1 atm
pressure are 1343 cal/mole and -4.91 cal/mole deg, respectively. What is
the G for the phase change at this temperature and indicate whether this
process is spontaneous?
The heat content or total energy of the system is then divided into interna
and external energy:
H =
Total
energy
Internal
energy
PV
External
energy
The total heat maybe divided into isothermally available or free energy
G and isothermally unavailable energy TS
H =
Total
energy
isothermally
available
energy
TS
isothermally
unavailable
energy
E =
Internal
energy
isothermally
available
internal
energy
TS
isothermally
unavailable
energy
G =
G =
G =
H - TS
E + PV A + PV
TS
Exercise
What is the free energy change when 1 mole of an ideal gas is compressed from 1
atm to 10 atm
Determine the change in the entropy, Helmholtz free energy, and Gibbs free
energy, when a mole of ideal gas is compressed from 1atm to 100 atm at 20C.
What is the free energy change when the kidneys transfer various chemical
constituents at body temperature from the blood plasma to the more
concentrated urine. The concentration of urea in the plasma is 0.005 mole/liter; in
the urine is 0.333 mole/liter. Calculate the free energy change in transporting 0.1
mole of urea from the plasma to the urine.
Exercise
If the molar concentration of a monomeric species of Sodium cholate at 25C is
4 x 10-3 mole/liter and the concentration of dimeric species is 3.52 x 10-5
mole/liter, what is the equilibrium constant and the standard free energy for the
dimerization process?