THERMAL EQUILIBRIUM interaction

between parts of the system causes no

further change in the system; same
temperature
INSULATOR

hinders/slows
down
interaction between systems (*ideal
insulator no interaction)
CONDUCTORS

permits
thermal
interactions through it
ZEROTH LAW OF THERMODYNAMICS - If
system C is in thermal equilibrium with
system A and B, then system A and B are
in thermal equilibrium.
LINEAR THERMAL EXPANSION formula is
valid only for small T (< 100 degrees)
VOLUME THERMAL EXPANSION - = 3
THERMAL STRESS developed when
object is hindered from expanding or
contracting
HEAT energy transferred due to
temperature change; always in transit
SPECIFIC HEAT heat energy needed to
raise the temperature of 1 kg of
substance by 1 degree
CALORIMETRY determine specific heat
of material
- Heat released by object = heat
absorbed by calorimeter
- Qout + Qin = 0
PHASE CHANGE takes place at definite
temperature; remains constant during
transition
LATENT HEAT FUSION melting/freezing
LATENT HEAT OF VAPORIZATION
evaporation/condensation
CONDUCTION heat transfer with bodies
in contact
HEAT CURRENT (H) describes flow of
heat (Watts)
CONVECTION heat transfer by mass
motion of a fluid from one region to
another
- H due to convection: directly
proportional to surface area
- Viscosity of fluids slow natural
convection near stationary surface
RADIATION transfer of heat by EM
waves
- H is proportional for surface area
- H increases rapidly with absolute
temperature (T4)

H depends on surface emissivity, e

(0<e<1)
- +Hnet net heat flow out of the
body
- blackbody (e = 1): good emitter,
good absorber
- reflectors: poor absorber, poor
emitter
STATE VARIABLES define state of a
material
- pressure, volume, number of
moles, temperature
IDEAL GAS EQUATION gas molecules:
treated as point particles
- do not interact with each other
- far apart and in rapid motion
- works best at high temperature
and low pressure
VAN DER WAALS EQUATION non-ideal
gases
MOLECULAR PROPERTIES OF MATTER
molecules interact, not point charge-like
- molecules are always in motion
- solids: vibrate around fixed points
- liquids: more free than solids
- gases: molecules free to move
around
- ideal
gas:
no
intermolecular
interactions
KINETIC MOLECULAR MODEL for ideal
gas
- Assumptions:
o Container with volume V
contains very large number N
of identical molecules, each
with mass m
o Molecules behave as point
particles, small compared to
size of container and average
distance between molecules
o Constant
motion,
elastic
collisions
with
wall
of
container (do not collide with
each other)
o Rigid and infinitely massive
container walls
- Pressure of gas comes from
collisions between container and
molecules

No. of collisions against an area of

the wall A after a small time
interval dt is:
1 N
A |v x| dt
2 V
- Total momentum change:
d p x =( of collisions)(dp x one molecule)
NAm v 2x dt
d px=
V
MOLECULAR SPEED root mean square
speed: average, not exact speeds
- Speeds are distributed based on
speed distribution function f(v)
- Maxwell-Boltzmann distribution
o Less than: value of fraction
o Greater than: 1 value of
fraction
o Between: difference of
fractions

( )

HEAT CAPACITY: GASES (J/mol-K) how

temp. changes when heat/energy is
added to the substance
- Add heat to ideal gas while keeping
gas volume constant: dQ = nCvdT
- Degrees of freedom = number of
velocity component needed to
describe the motion of a molecule
completely
- Equipartition theorem each
degree of freedom has KE per
molecule of 1/2kT
HEAT CAPACITY: SOLIDS (J/mol-K) Dulong-Petit Law
PHASE DIAGRAMS Triple point, phase
equilibrium, critical point (no phase
change, smooth properties change)
THERMODYNAMIC SYSTEMS collection
of objects that exchange energy with
environment
- Thermodynamic process change
in state of thermodynamic system
- Sign convention:
o (+) Q heat added to the
system, heat flows into
system, ((heat absorbed by
system))
o (-) Q heat taken from the
system, heat flows out of the

system, ((heat released by

system))
o (+) W work done by system
against surroundings, energy
leaving system, ((expansion))
o (-) W work done on system
by
surroundings,
energy
entering
system,
((compression))
WORK DONE DURING VOLUME CHANGES
area under a curve on pV-diagram
PATHS
BETWEEN
THERMODYNAMIC
PROCESSES work done by system does
not depend only on initial and final states
but also on the path
THERMODYNAMIC PROCESSES:
- Isobaric constant pressure
- Isochoric constant volume
- Isothermal constant temperature
- Adiabatic zero heat
INTERNAL ENERGY (U) Sum of KE + PE
- State variable
- First Law of Thermodynamics
- U path-independent
- unique for every thermodynamic
system
CYCLIC PROCESSES initial = final state
- change in internal energy is zero
- usually used in engines
ISOLATED SYSTEM constant internal
energy
INTERNAL ENERGY OF AN IDEAL GAS - U
is dependent only on temperature, not on
pressure or volume
HEAT CAPACITIES: CONSTANT P/V heat
capacity of substance depends on
conditions under which heat is added;
*isobaric: Cp
** For an ideal gas, the change in internal
energy for any process (constant volume
or not):
U =n C V T
ADIABATIC PROCESSES no heat
exchange
between
system
and
surroundings (Q = 0)
- adiabatic heating raising T, Q=0
- adiabatic cooling lowering T, Q=0
- Q = 0, U = -W
THERMODYNAMIC PROCESSES
- Direction: reversible vs. irreversible

Reversible: infinitesimal changes

from equilibrium; quasi-static and
quasi-equilibrium
- Disorder:
affects
direction
of
processes;
added
E
makes
molecules behave differently
HEAT ENGINES device that transforms
heat partly into work or mechanical
energy; cyclic process
RESERVOIRS absorb from high temp.,
release at low temp.
- Hot reservoir: Source
- Cold reservoir: Sink
ENERGY
FLOW
DIAGRAMS/ENERGY
RESERVOIR MODELS
EFFICIENCY (e) energy is conserved;
ideal efficiency = 1
INTERNAL-COMBUSTION
ENGINES

commonly used in gasoline engines

- Define: compression ratio (r)
OTTO CYCLE cyclic process:
1.) Adiabatic compression
2.) Isochoric heating (heat in)
3.) Adiabatic expansion
4.) Isochoric cooling (heat out)
- Efficiency (e) = 1 r 1
DIESEL CYCLE cyclic process:
1.) Adiabatic compression
2.) Isobaric expansion
3.) Adiabatic expansion
4.) Isochoric cooling
- More efficient than Otto engines
REFRIGERATORS heat engine operating
in reverse
- Importance of work since heat
transfers from hot to cold
- 2 systems: interior, exterior
2ND LAW OF THERMODYNAMICS
- Kelvin-Planck statement: It is
impossible for any system to
undergo a process in which it
absorbs heat from a reservoir at a
single temperature and converts
the
heat
completely
into
mechanical work, with the system
ending in the same state in which it
began.
o 100-% efficient engine is
impossible!
- Clausius statement: It is impossible
for any process to have as its sole

result the transfer of heat from a

cooler to a hotter body
o Workless refrigerators are
impossible
CARNOT ENGINE hypothetical, idealized
heat engine that has the maximum
possible efficiency (consistent w/ 2nd law
of thermodynamics)
- avoids all irreversible processes
- cyclic process:
o Isothermal
expansion
(Absorbs heat)
o Adiabatic expansion
o Isothermal compression at Tc
(release heat)
o Adiabatic compression
- Most efficient engine
CARNOT REFRIGERATOR reverse of
Carnot engine
- Have
the
maximum
possible
coefficient of performance
THIRD LAW OF THERMODYNAMICS it is
impossible to reach absolute zero in a
finite number of steps
ENTROPY, S (J/K) disorder (movement of
molecules)
- Path-independent
- Total entropy change during any
reversible cycle is zero
- Irreversible processes: increase
entropy
- When all systems taking part in a
process are included, the entropy
either
remains
constant
or
increases.
- Total change in entropy should not
decrease

Reversible cyclic process:

S system =0,
S surrounding=0,
Suniverse =0
Irreversible cyclic process:
S system =0
S surrounding >0
Suniverse >0
*Freezing of water:

 S system <0

but S surrounding >0

Suniverse 0
MICROSTATES looks at individual
- macrostates look at whole
- same macrostate for different
microstates

Second law: The most probable

macroscopic state is the one with
the
greatest
number
of
corresponding microscopic states.
o Said macroscopic state has
the greatest entropy