5/15/2020 Chemical Thermodynamics (chap 19) Flashcards | Quizlet

Chemical Thermodynamics (chap 19)

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Terms in this set (26)

Enthalpy heat transferred b/w the system and its

surroundings during a constant-pressure
process

First Law of energy is conserved

Thermodynamics -energy is neither created or destroyed,
only transferred and/or converted

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-total energy of universe remains

constant
∆E= q+w

Spontaneous Processes -proceeds on its own without any

outside assistance
-occurs in one direction only
-reverse is nonspontaneous
-often depends certain conditions such
as temperature and pressrue
-doesn't have to be fast
-thermodynamics tell us about the
direction and extent of a reaction, but
nothing about the rate (rate=kinetics)
-many exothermic reactions are
spontaneous, however, there are also
spontaneous endothermic rxns and thus
there is more in determining spontaneity

Reversible Process -a specific way in which a system

changes its state
-the change occurs in such a way that
the system and surroundings can be
restored to their original states by
exactly reversing the change
-can restore system to its original
condition with no net change to either
system or surroundings
-a reversible change produces the max
amount of work that can be done by a
system on its surroundings
-reversible processes are those that
reverse direction whenever an
infinitesimal change is made in some
property of the system
-If a system undergoes a reversible
process, the change in entropy of the
system is exactly matched by an equal

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and opposite change in the entropy of

the surroundings

Irreversible Process -cannot simply be reversed to restore

system and its surroundings to their
original states
-if the same path cannot be followed to
restore the system to its original state
indicates that a process is irreversible
-any spontaneous process is irreversible
(b/c reverse always requires work)

Isothermal Process -occurs at constant temperature

Entropy (S) -associated with the extent of

randomness in a system or the extent to
which energy is distributed among
various motions of the molecules of the
system
-state function; characteristic the state
of the system
-thus ∆S depends only on the initial and
final states and not on path. ∆S= S(final) -
S(initial)
-for isothermal process: ∆S= q(rev)/T
(can be used for any isothermal process,
not just reversible one)
-∆S for phases changes (isothermal): ∆S=
∆H(fusion)/T
-increase in randomness or disorder of
system, or increased dispersion of
energy

The Second Law of - ∆S(univ) = ∆S(sys) + ∆S(surr)

Thermodynamics - any irreversible process results in an
increase in entropy of the universe,
whereas any reversible process results in

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no change in the entropy of the universe

-the entropy of the universe increases in
any spontaneous process

Microstate -is a single possible arrangement of the

position and kinetic energies of the
molecules when the molecules are in a
specific thermodynamic state

Boltzmann Equation S=klnW

-k is boltzmann constant, 1.38x10^23 J/K
-each thermodynamic state has a
characteristic number of microstates, W
-entropy is a measure of how many
microstates are associated with a
particular macroscopic state
- ∆S = k ln(Wfinal/Winitial)
-any change that leads to an increase in
the number of microstates leads to a
positive value of ∆S
-entropy increases with the number of
microstates of the system

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