Potential Energy

o Elastic Potential Energy = (1/2)k(x^2)

o Gravitational Potential Energy = mgh
o

Chemical Potential Energy =

q1q2
4 0 r

Thermodynamics
o The study of energy and energy changes.
Defining a System
o System = Part of the universe that we are studying.
o Surroundings = The rest of the universe that we are not studying.
o Boundary = Separation between the system and the surroundings
It can either be a real or imaginary separation.

Surroundin
gs

Syste
m

Bounda
ry

Types of Systems
Type of System
Open
Closed
Isolated
Exchanges matter
Yes
No
No
with surroundings?
Exchanges energy
Yes
Yes
No
with surroundings?
Equations of state
o State variables are not indeoendant the relationships etween state
variables are descrived by eqyations of state
o Equations of state apply only to systes that are at equilibrium.
o An important example is the ideal gas equation.
Internal Energy (E or U)
o Internal energy (E) is a state variable.
o The internal energy of a system is the sum of the kinetic and potential
energies of all its components.
o Internal energy includes:

Translational energy
Vibrational energy
Rotational energy
Intermolecular interactions
Intramolecular interactions (e.g. bonds between atoms)
Energy arising from the relative positions of electrons, neutrons,
and protons
First Law of Thermodynamics
o Energy of the universe is conserved.

o
o

Euniverse =0= E system + E surroundings

How is energy transferred?

Energy is transferred as hear or as work.

E=q+w

q=heat ; w=work

Process
Work done on the system
by the surroundings
Work done by the system
on the surroundings
Hear released from the
system to the
surroundings
Heat absorbed by the
system from the
surroundings

Sign of work (w)

+
-

Sign of heat (q)

N/A
N/A

N/A

N/A

Path dependence.
o State variables
The value of state functions does not depend on the path taken
to reach that specific function or value.
o Path variables
The value of state functions does depend on the path taken to
reach that specific function or value.
How does the path affect the work done?
o In CHEM 123 we will focus on pressure-volume (PV) work.
o From physics:

W = Fdx

dw=
F d x

Popposing =

dw=
F d x =Popposing Ad x =P opposing dV

F
A

F=Popposing A

V2

w= PdV
V1

At constant opposing pressure

In CHEM 123, we will mostly talk about work at constant

opposing pressure.
1) The math is easier.
2) Many reactions are done at a constant pressure.

For an ideal gas, if

Fast expansion

w=P opposing V

E=q+ w=0 ; q=w

w=P 2 V =A

q= A

Endo and exothermic

o When heat flows out of a system during a reaction, q < 0 so delta H <
0 and we call the reaction exothermic.
o Opposite for endothermic
Summary
o Energy cant be measured directly, but we can measure work and heat.
o Heat is easy to measure using calorimetry
o The heat at constant volume, q, gives us a measure of delta E
o Most chemistry however, is carried out at constant pressure.
o We define a new state variable, Enthalpy.
How can we measure delta H directly?
o Since delta H = q, we can measure delta H using constant-pressure
calorimetry.
o Measure q is relatively easy but having to measure it for every single
reaction is a pain.
How can we know H? Does it matter?
o Enthalpy is defined as H = E PV, Just like with E, knowing the value of
H for a given state is difficult.
Hesss Law
o The heat of reaction for a specific reaction is equal to the heats of
reaction for any set of reactions which in sum are equivakent to the
overall reaction.
Solving a Hesss Law Problem
o Hunt: Hunt for an alternate route from reactants to products using
steps with known enthalpy data.
o Establish signs: Flip the sign of delta H for any reaction you reverse.
o Stack: Write out the steps one over the other, with delta H on the right
hand side.
o Stoichiometry: Adjust the stoichiometry so that all special that arent in
the overall equation of your reaction of interest will cancel out (if you
multiply a reaction by x, multiply delta H by x too)

Sum: Add the delta H values on the right to get the delta H for your
reaction of interest.