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General Summary of Thermodynamics
FIRST LAW OF
THERMODYNAMICS:
The total amount of energy (and
mass) in the universe is constant.
That is, in any process energy can
be changed from one form to
another; but, it can never be
created nor destroyed.
“ You can’t get something for
nothing”
SECOND LAW OF
THERMODYNAMICS:
In any spontaneous process the
entropy of the universe increases:
Suniverse = Ssystem + Ssurroundings
or
Suniverse -Ssurroundings = Ssystem
(Variant)In trying to do work, you
always lose energy to the
surroundings.
“You can’t even break even!”
THIRD LAW OF
THERMODYNAMICS:
Any pure crystalline substance at
a temperature of absolute zero
(0.0K) has an entropy of zero
(S = 0.0 J/K-mol).
Terminology:
Energy = capacity to do work
System = portion of the universe we are considering
Open system = energy and matter can transfer
Closed system = energy transfers
Isolated system = no transfers
Surroundings = everything else besides the system
Isothermal = system at constant temperature
Heat capacity = amt. of heat required to raise the temperature of a
certain amt. of material by 1C or 1K.
Calorie = amt. of heat required to raise the temperature of 1g of water
by 1ºC.
Signs:
H >0 or (+) heat absorbed (endo)
H <0 or (-) heat released (exo)
S >0 or (+) entropy increasing (becoming disordered)
S <0 or (-) entropy decreasing (becoming ordered)
G >0 or (+) nonspontaneous Kc <1
G = 0, Kc = 1
G < 0 or (-) spontaneous Kc >1
Rules about Entropy: (Entropy increases)
1. w/ increasing temperature*
2. as one goes from s -> l -> aq ->g*
3. if a solid or liquid is dissolved in a solvent*
4. number of particles increases*
5. mass of the molecule increases
6. Entropy is higher for weakly bonded materials than for strong
covalent materials
7. As complexity of a molecule increases.
FORMULA’S:
G = H- TS (T in K = 273 + C)
T = H/S (assume G = 0 or when Kc = 1, like fusion/vaporization)
Hrxn = (#mol.) *(Hf(products)) -.
5. FIRST LAW OF
THERMODYNAMICS:
The total amount of energy (and
mass) in the universe is constant.
That is, in any process energy can
be changed from one form to
another; but, it can never be
created nor destroyed.
“ You can’t get something for
nothing”
SECOND LAW OF
THERMODYNAMICS:
In any spontaneous process the
entropy of the universe increases:
6. ndings
or
-
(Variant)In trying to do work, you
always lose energy to the
surroundings.
“You can’t even break even!”
THIRD LAW OF
THERMODYNAMICS:
Any pure crystalline substance at
a temperature of absolute zero
(0.0K) has an entropy of zero
(S = 0.0 J/K-mol).
Terminology:
Energy = capacity to do work
System = portion of the universe we are considering
Open system = energy and matter can transfer
Closed system = energy transfers
7. Isolated system = no transfers
Surroundings = everything else besides the system
Isothermal = system at constant temperature
Heat capacity = amt. of heat required to raise the temperature
of a
certain amt. of material by 1C or 1K.
Calorie = amt. of heat required to raise the temperature of 1g
of water
by 1ºC.
Signs:
-) heat released (exo)
-) entropy decreasing (becoming ordered)
-) spontaneous Kc >1
Rules about Entropy: (Entropy increases)
1. w/ increasing temperature*
2. as one goes from s -> l -> aq ->g*
8. 3. if a solid or liquid is dissolved in a solvent*
4. number of particles increases*
5. mass of the molecule increases
6. Entropy is higher for weakly bonded materials than for strong
covalent materials
7. As complexity of a molecule increases.
FORMULA’S:
-
fusion/vaporization)
-
oducts)) -
-> J to kJ)
-
-RTlnKc or Kc = e
-
Remember: e
x
is 2
nd
function natural log (ln) on calculator and work inside-out
9. + + (+/-
- + - (Spontaneous at ALL Temperatures)
- - (+/-
+ - + (Non-spontaneous at ALL Temperatures)
- – gives a spontaneous
reaction
q is the heat measured from a reaction. If rxn is at constant
pressure q = H
q is measured experimentally by calorimetry where qsystem = (-
)qsurroundings
here you maybe calc qsys,
if qsystem = positive number (absorbing heat) it comes from the
surroundings where
qsystem = (-)qsurroundings
Hess' Law: The addition of several reactions to obtain a
10. "desired" overall reaction. If a reaction
multiplied by a coefficient, then also
appear on both sides of the
equation and do not appear in the "desired" equation.
Enthalpy is a stoichiometric quantity: The amount of heat is
proportional to the number of
moles of reactants/products.
Entropy: The measure of disorder of the system.
Entropy can NOT be experimentally measured directly.
1
st
, look for changes in physical states (s, l, aq, g) from reactants
to products.
2
nd
, look for changes in the number of moles of reactants to moles
of products.
11. Standard States Conditions:
Solution
s: 1 M; Partial Pressures: 1 atm;
Temperatures are generally at 25°C (298 K)
Gibbs' Free Energy: Amount of
“price” one must pay to do work.
Enthalpy, Entropy, and Gibb's Free Energy are all state
functions. State functions depend only
on the final and initial states of a process.
So also calcul
(products) - initial state (reactants).
Consider non-equilibrium conditions:
One can calculate Gibb's Free Energy for non-equilibrium
conditions using Q from Equilibium
Chapter:
12. - ) move toward
becomes less positive until it reaches zero-equilibrium.
- RT ln(K) (where R =
8.314 J/(Kmol) and K = equil.
constant (WATCH OUT for units: R has units Joules, but
where 1000 J = 1 kJ.
Thermodynamic Data at 298.15 K (25°C)
