Getting Started: Some Terminology

• System - defined by Open Closed Isolated

its interactions with water vapour leaving

stopper = tea
cannot escape no possibility that energy can

its... = losing matter be transmitted to its

surrounding

• 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

Whether simple or Text

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).

As evident from this plot of He

(0.010 mol) behaviour as f(P,V,T),
we can fit these curves to
Fixed amount of gas and temp

PV = αT - bigger volume = lower pressure

Inverse relationship

α is proportional to the mass of

gas used, so α = nR , and
PV = nRT

These variables work

together to define a
system’s state through an
equation of state, such as
the Ideal Gas Law,

PV = nRT

that we use to describe the

state of the gas under any
conditions of (P,V,T),
 These variables work
together to define a
system’s state through an
equation of state, such as
- PV = nRT
volume is the size
the Ideal Gas Law,
all variables have a lower limit of zero
pressure: impossible to have negative values
n = # of moles
R = ideal gas constant PV = nRT
T = temperature (in K) P,V,n,T are the variables
R is a constant
that we use to describe the
state of the gas under any
conditions of (P,V,T),

like the state of the system in

this chamber...

...or to compare states of different systems, such as the two

here, that even though they have identical numbers of
components and are in identical chambers, have different
pressures and temperatures, hence are in different states.
 adiabatic wall = no exchange of anything
- no energy exchange
ISOLATED SYSTEM

If we bring these two

chambers into contact, so
that they share one
impermeable wall (no
exchange of matter), we
can observe any changes
that occur over time.
impermeable, no exchange of matter

If the systems stay like this, with different pressures and

temperatures even after an extended time, we call the wall
adiabatic as it allows no exchange of energy between the
systems.

eventually pressure becomes the same..

non-adiabatic = diathermal

If, however, over time

the systems exchange
energy so that they end
up in identical states, the
wall is called diathermal
(or nonadiabatic), and it
allows the two systems
to reach thermal
equilibrium, i.e., their
temperatures and
pressures become
equal.

At equilibrium, there will be no further changes to these

systems as long as we do nothing further to them.
First Law
- system is isolated (no exchange of matter or energy)
- law of conversation of energy in a closed system
- only worries with quantity not direction

The Laws of Thermodynamics

Zeroth Law
• Zeroth Law: Two systems that are separately in thermal - once we calibrate the 3rd
system with known temperature
equilibrium with a third system are also in thermal of somewhere else, then we can

equilibrium with one another. use it to measure the

temperature of the other
systems without having the
• First Law: The internal energy, U, of an isolated system is calibration from the 3rd system
constant. (i.e. thermometer)

• Second Law: It is impossible for a system to undergo a

cyclic process whose sole effects are the flow of heat into
the system from a heat reservoir and the performance of an
equivalent amount of work by the system on the
surroundings.
• Third Law: The entropy of a pure, perfectly crystalline
substance (element or compound) is zero at 0 K.

The Concept of Temperature

Using the Ideal Gas Law,

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.

all meet at a common point

that is the thermal dynamic limit
Q: Why is Celsius 0-100?
A: took the phase change temps and make it 0-100 Temperature in C
01_03fig_PChem.jpg
So we can use
T(K) = T(°C) + 273.15

or by convention,
T(K) = 273.16 P/Ptp

(Ptp - P at triple-point of water)

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.

Simplest approach is to use ntotal, but....

• Partial pressure
–Each component of a gas mixture exerts a
pressure that it would exert if it were in the
container alone. Need assumption of ideal gas
1. take up no space/volume (no need to exclude volume due to size of particles itself)
2. particles do not interact (no attraction or repulsion)
then we can say gases behave the same alone or with other gases
Dalton’s Law of Partial Pressure

+ =

The total pressure of a mixture of gases is the sum of

the partial pressures of the components of the mixture.

Refer to example on page 9-10 in textbook

Work through Example 1.2 in the textbook for practice

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

2) the finite size of,

particles occupy space
- dip degree depends on the kind

the atoms or molecules that of particle

make up the gas. repulsive wall: once it starts going

up (dont want to be squeezed too
tight together)

So it ignores both attractive

and repulsive forces that are ideal gas area: if real gas has
enough room / lots of space, it
part of any real gas system. will behave like ideal gas

if real gasses are brought close

to each other with high pressure
or low temperature, then it
behaves like real gas

Nonideal (Real) Gases

at 400K
H2
represented by a z Compressibility factor PV = 1 for an ideal gas at 400K, no interaction that
nRT
if z = 1, gas behaves like ideal gas collapse them together. Not
Deviations occur for real gases. enough electrons to create
attraction. Only size so no
PV
> 1 - molecular volume is significant. negative dip
nRT
pressure is larger than ideal gas we predicted (size is a O2
factor of behaviour of particples more electrons =
PV more dipole IMF
< 1 - intermolecular attractive forces. size takes over and
nRT pulled together by IMF
at 0 pressure, all higher pressure it
gasses start at ideal crosses 1
z < 1 because pressure drops
CO2
Text lots of dipole = lots of
attractive interaction
(big dip)
size takes over and
higher pressure it
croses 1
 The van der Waals
Equation of State
tries to take key assumptions and correct it
account of attractive interaction of particles and size of molecules

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

a and b are molecule-dependent constants:

a – provides a measure of the strength of intermolecular forces
b – provides a measure of the sizes of molecules
a and b depend on identity of gas you’re working with
a and b are not constants

van der Waals Parameters

examples of a and b constants depending on the molecule

Gas a (L2 bar mol-2) b (L mol-1)

H2 0.24646 0.026665
O2 1.3820 0.03186
CO 1.4734 0.039523
CO2 3.6551 0.048216
C5H12 19.124 0.14510

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

– Many ways it can be stored in a system.

• Kinetic Energy
– The energy of motion.
• Potential Energy Energy that is stored and waiting to be released
example: dropping a ball, release ball = release trigger = ball drops

– Energy due to condition, position, or composition.

– Associated with forces of attraction or repulsion
between objects.
• Energy can change from potential to kinetic.

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

• First Law: The internal energy, U, of an isolated system is

constant.
Also called Law of Conservation of Energy
example: universe is isolated system
with constant U ΔUtotal = ΔUsystem + ΔUsurroundings = 0
Of universe cut out tiny part something has to change in opposite direction to keep total U constant
ΔUsystem = -ΔUsurroundings
change in system = equal and opposite for surrounding
A system contains only internal energy U. It only changes by:
A system does not contain heat and work but
contains energy that can be converted/transferred
ΔU = q + w q and w represent energy being transferred!
calculates how much q and w it can do, but does no t exist at rest
A system does not contain heat (q) or work (w) - these only occur
during a change in the system.

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

NOTE: 1 “calorie” of food represents 1 kcal of energy

Heating a Substance at Constant

P
When we heat a substance, two things can happen: the temperature increases, or a
phase change occurs.

Tf

warming
vapour ∆Tgas
note that the slopes are different (depending on how well it absorbs energy)

Tvap = liquid/gas Tvap vaporizing liquid

Start off as block of ice -> increase temperature

warming
liquid ∆Tliquid
phase change = isothermal process
temperature does not change during phase change
note: energy is still being put into it but goes into breaking molecule interaction instead of increase thermal motion
Tfus = gas/liquid Tfus melting solid

∆Tsolid conversion finished, temperature increases

Ti Qgas
Qsolid Qfus Qliquid Qvap
warming
solid

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

–Molar heat capacity, C. q = nCΔT only for pure substances

• System is one mole of substance.

–Specific heat capacity, c. q = mcΔT per gram (not per mole)

• System is one gram of substance

–Heat capacity q = CΔT
• Mass × specific heat, or
• For a device like a calorimeter

Note on Molar units

• The textbook indicates molar units, like
molar heat capacity or molar volume, with a
subscript m, e.g., Vm or CP,m
• I’ll use the more conventional symbolism,
with an “overline” indicating a molar quantity,
e.g., V or CP

29
 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).

only have temperature going up work being one (pushing it up)

temperature being the other (increasing/going up)

Heat Capacities CP of Simple Substances

 Heat Capacity Varies with T

q = C∆T Text

Heat Capacity Varies with T

energy entering system
q positive
c always positive
dT has to be positive too
Tf
q=∫ CdT
energy leaving system Ti
q negative
c always positive
dT will be negative too
 Work work and heat are energy transfers

• In addition to heat effects chemical reactions

may also do work.
• Work is defined as force acting over a
distance

! Gas formed pushes

against the atmosphere.
! Volume changes.

Pressure Volume Work

nothing opposing movement
force = mass x acceleration = (kg/m^2)
of piston

w=F×d delta h = change in height/distance

= (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

∆U system < 0 ∆U system > 0

State Functions and Path Functions

state function vs path function?

• Any property that has a unique value for a specified

state of a system is said to be a State Function.
- e.g., for water in a specified state, at 293.15 K and 1.00 atm,
density is a unique function of state
its density d = 0.99820 g/mL condense steam to 20C -> density is the same
history of how to get water to 20C does not matter. the water at 20C will always be the same
- This density is a unique function of the state.
- It does not matter how the state was established.
• Changes in heat and work are not functions of
state - they depend on the path taken, so are called
Path Functions
how it got there is relevant (can have extra work done before reaching the same state)
 Functions of State
• U is a function of state.
–Not easily measured.
• ΔU has a unique value between two states.
–Is easily measured.
cyclic change = 0
state 1 -> state 2 -> state 1 — change of U = 0

Since U is a state function, it satisfies the following

equation: 2
∆U = ∫ dU = U 2 − U 1
1
and dU is called an exact differential.
exact differential is a state function

Any state function, including U, also

satisfies the cyclic integral:

∮ dU = U 1 − U 1 = 0
cyclic change = 0
state 1 -> state 2 -> state 3 -> state 1 — change of U = 0

showing that there is no net change in the state function if

the initial and final states are the same, regardless of path.
 Path Functions
Consider the expansion of 0.100
mol He gas at 298 K when one
of two masses, each equivalent
to a constant external pressure
of 1.20 atm, is removed
where does he get his volumes from? PV = nRT

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

NOT THE SAME AMOUNT OF WORK - PATH-DEPENDENT!

Irreversible vs Reversible Expansions

If the driving force for a
particular “path” is reversed,
and as a consequence the
changes it causes are
reversed, we can consider
that process reversible.
Think of replacing large
masses with grains of sand...

A reversible process takes

many small steps (and more
work!)
Irreversible vs Reversible Expansions
If the driving force for a
particular “path” is reversed,
and as a consequence the
changes it causes are w = −P∆V
reversed, we can consider 1st step

that process reversible.

step 2
It is readily seen in these 1 step process
indicator diagrams of P vs V.

A reversible process takes

many small steps (and more whole area of curve = tiny change in pressure, tiny change in volume
^ find the integral
work!)

Irreversible vs Reversible Expansions

If the driving force for a
particular “path” is reversed,
and as a consequence the
changes it causes are w = − ∫ PdV
reversed, we can consider
that process reversible.
It is readily seen in these
indicator diagrams of P vs V.

A reversible process takes reversible has more work

^ infinite number of reversible step

many small steps (and more

work!)
 Irreversible vs Reversible Expansions

The most work can be extracted from a reversible

expansion, indicated by red area under the curved lined.
Irreversible expansions, given by sudden changes in
pressure, yield less work, clear from the yellow areas, but
increasing the number of steps makes it closer to reversible.

Irreversible vs Reversible Compressions

irreversible compression takes more
work if we do less step

reversible compression takes the

least amount of work

opposite for expansion

It takes less work to complete a reversible compression,

indicated by the area under the solid curved lined.
Irreversible compressions, given by sudden changes in
pressure, require more work, clear from the green areas
extending beyond the line of reversibility, but increasing the
number of steps makes it closer to reversible.
 Constant Volume vs Constant Pressure
Initial state → Final state
Ui Uf
ΔU = Uf - Ui
ΔU = q + w
In a system at constant volume:
ΔV = 0 so wV =0
ΔU = q + 0 = qv
constant volume so work = 0
change in state (for U) is identical at
q defined path of constant value
constant volume and pressure
But we live in a constant pressure world!
How does qp relate to qv?

Constant Volume vs Constant Pressure

qV = q P + w
We know that w = - PΔV and ΔU = qV, therefore:
ΔU = qP - PΔV
qP = ΔU + PΔV replaced path functions with state functions

These are all state functions, so define a new function, enthalpy.

Let H = U + PV
since all variables are state functions, we can have new variable H as new state function variable

Then ΔH = Hf – Hi = ΔU + ΔPV
( )

If we work at constant pressure and temperature:

ΔH = ΔU + PΔV = qP
Internal Energy U vs Enthalpy H

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

How do these quantities fit together?

• U and H are f(T)
∆U = q V = C V (T f − T i )
∆H = ∆U(T) + ∆(PV) = ∆U(T) + ∆(nRT) = ∆H(T)
∆H = q P = C P (T f − T i )

• 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
51
 How do these quantities fit together?
Some useful things to remember...

• Because ∆U and ∆H depend only on T, they equal 0 for an

isothermal process. if delta T = 0 then delta U and delta H are 0

• q = 0 for an adiabatic process, as no heat is transferred.

= no transfer of heat (thermos) so q = 0

• If only expansion work is possible, w = 0 for a constant

volume process.

52

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

Expansion/Compression of an Ideal Gas

• It’s important to adiabatic curve
temperature goes up = pressure goes up

remember the difference remember why adiataic has higher pressure

between adiabatic and

isothermal processes
– Isothermal - heat is
transferred to keep T the
same between system and adiabatic curve

surroundings tries to grab more energy but adiabatic so

takes energy from temperature

– Adiabatic - heat is trapped drop in temperature so drop in pressure

remember why adiabatic is lower
on either side of the
boundary so T rises or falls
within the system

53