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Getting Started: Some Terminology: - System
Getting Started: Some Terminology: - System
• Surroundings -
everything else in the tip it over, matter will
not spill out
universe that isn’t the
system
can exchange energy
• Can be simple... cannot exchange matter
Or complex!
Boundaries
complex, the
interface between
the system and
surroundings is
called the boundary,
which can be as
simple as the air-
liquid interface in a
glass of water, or
the cell walls in
these examples of
open systems.
Once we define the system,
we need to describe its state.
We do this using macroscopic
system variables, such as pressure
(P), temperature (T), Volume (V) or
number of moles (n).
PV = nRT
PV P
T= =
nR ρR Temperature and pressure
is linear for a given volume
n
where the molar density ρ =
V
So a plot of P vs T extrapolated
back to the x axis yields a lower limit
to temperature, -273.15°C, which
defines absolute zero, or 0 K.
or by convention,
T(K) = 273.16 P/Ptp
to define an absolute
temperature scale and use
this to define temperature
as a tool to measure
thermal equilibrium.
01_05fig_PChem.jpg
Mixtures of Gases
Gas laws apply to mixtures of gases.
+ =
01_ex02_PChem.jpg
Real vs Ideal Gases
Ideal Gas Law ignores
1) intermolecular attractions - real gas particle follow red line
- attractive forces causes the dip
between, and pulling up, size takes over and
n 2a
P+ 2 V – nb = nRT
V
weakness: for O2, it is alright because O2 is uniform. However, depending on
the orientation of H2O molecule interaction, the number can change
This is not the only way to describe real gases - there are
many others - but we’ll wait till Chapter 7 to deal with them.
Energy - some terminology
• Internal Energy, U Internal energy: total sum of all energy in the system
Internal Energy, U
Total energy (potential and kinetic) in a
molecular system.
Translational kinetic energy.
Molecular rotation.
This is really hard to quantify
Bond vibration.
Intermolecular attractions.
Chemical bonds.
Electrons.
The Laws of Thermodynamics
Heat
Energy transferred between a system and its
surroundings as a result of a temperature
difference.
• Heat flows from hotter to colder.
–Temperature may change.
–Phase may change (an isothermal process).
Units of Heat
• Calorie (cal)
–The quantity of heat required to change the
temperature of one gram of water by one
degree Celsius. (outdated units)
• Joule (J)
–SI unit for heat
1 cal = 4.184 J
1 cal of food = 1000 cal = 4184J
Tf
warming
vapour ∆Tgas
note that the slopes are different (depending on how well it absorbs energy)
Q
Heat Capacity
• The quantity of heat required to change the
temperature of a system by one degree.
the bar on top of C represents a molar quantity variable
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Heat Capacity
Generally, there are two conditions under
which we measure thermodynamic quantities
like heat capacity - either at constant volume
(giving CV) or at constant pressure (giving CP).
q = C∆T Text
= (m × g) × Δh × A
isothermal state, no change in heat A = area of piston
temperature is constant A
no need to worry about heat capacity force / area = pressure
= PΔV
w = -Pext ΔV
positive change in volume, work is negative
act against surrounding and pushing surrounds back
energy is leaving the system
measure work done by
measuring distance energy leaving system -> work is negative
energy is put into the system -> work is positive
when not constant external pressure
Energy
• Kinetic Energy (units : Joules, J)
2
1 m
ek = mv2 [ek] = kg = J
2 s
• Work (units : Joules, J)
kg m m = J
w = Fd [w] =
s2
First Law of Thermodynamics
∮ dU = U 1 − U 1 = 0
cyclic change = 0
state 1 -> state 2 -> state 3 -> state 1 — change of U = 0
w = −P ext ∆V
= −(1.20 atm)(2.04 − 1.02 L)
= −1.22 L atm
= −124 J (since 1 L atm = 101.325 J)
Path Functions
Now consider a similar expansion
of 0.100 mol He gas at 298 K
when one, then a second, of four
masses, each equivalent to a
constant external pressure of
0.60 atm, is removed.
w = −P ext ∆V
= −(1.80 atm)(1.36 − 1.02 L) − (1.20 atm)(2.04 − 1.36 L)
= −1.43 L atm
= −144 J (since 1 L atm = 101.325 J)
the internal energy change is the same as example before but more work is done
Path Functions
vs.
more steps = more work
w = −124 J w = −144 J
Then ΔH = Hf – Hi = ΔU + ΔPV
( )
qP = -566 kJ/mol
= ΔH
PΔV = P(Vf – Vi)
work
= RT(nf – ni)
= -2.5 kJ
ΔU = ΔH - PΔV
= -563.5 kJ/mol
more heat leaving system = qV
because work is also being done
• Work w = − ∫ P external dV
– If Pexternal = constant
w = −P external (V f − V i )
– If the process is reversible
nRT
w = −∫ dV
V
– If reversible and isothermal dV Vf
w = −nRT ∫ = −nRT ln
V Vi
isothermal so T is a constant
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How do these quantities fit together?
Some useful things to remember...
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adiabatic:
T is not constant
all T is trapped
Adiabatic vs Isothermal
compress a balloon -> work being on onto system
u = (q=0) + increase work
energy is trapped so transfers to temperature going up = equilibium with surrounding and temp is constant
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